TW201903049A - Liquid crystal alignment agent, method for producing liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

A liquid crystal alignment agent which is capable of forming a liquid crystal alignment film with fast reaction speed and high impedance, the production method for the liquid crystal alignment film formed from the liquid crystal alignment agent, and a liquid crystal display element having the same are provided. The liquid crystal alignment agent includes a polymer (A) a photo alignment polysiloxane (B) and a solvent (C). The polymer (A) is obtained by reacting a first mixture includes a tetracarboxylic dianhydride component (a1) and a diamine component (a2). The photo alignment polysiloxane (B) is obtained by reacting a polysiloxane (b1) including an epoxy group with a cinnamic acid derivative (b2) and an ethylenically unsaturated compound (b3).

Description

Liquid crystal alignment agent, method for manufacturing liquid crystal alignment film, and liquid crystal display element

The present invention relates to a liquid crystal alignment agent, a method for manufacturing a liquid crystal alignment film, and a liquid crystal display element, and more particularly, to a liquid crystal alignment agent capable of forming a liquid crystal alignment film with a fast response speed and a high bulk impedance, and formed of the liquid crystal alignment agent. A method for manufacturing a liquid crystal alignment film and a liquid crystal display element including the liquid crystal alignment film.

With the development of liquid crystal displays toward large-sized display specifications, in order to overcome the problem of viewing angles in large-sized displays, the wide-viewing angle technology of liquid crystal display panels must also continue to improve and breakthrough. Multi-domain vertical alignment (MVA) liquid crystal display panel is a common wide-viewing angle technology. A multi-domain vertical alignment type liquid crystal display panel is a liquid crystal alignment film formed in a liquid crystal panel. The liquid crystal alignment film is a protrusion, which can limit the direction in which liquid crystal molecules are tilted, thereby achieving a wide viewing angle display effect. However, the liquid crystal display panel of the multi-domain vertical alignment type cannot avoid problems caused by insufficient transmittance and contrast of the protrusions and slow response of liquid crystal molecules.

In order to solve the above problems, a polymer stabilized alignment (Polymer Sustained Alignment, PSA) technology has been developed. This technology uses a gap between a pair of substrates composed of a substrate with a patterned conductive film and a substrate without a patterned conductive film, or a pair of substrates composed of two substrates with a patterned conductive film. A liquid crystal composition containing a polymerizable compound is sandwiched between the gaps, and the liquid crystal composition is irradiated with ultraviolet light to polymerize the polymerizable compound while a voltage is applied between the conductive films, thereby exhibiting a pretilt angle characteristic and controlling the liquid crystal. Alignment direction. This technology enables the conductive film to form a specific structure, thereby achieving the effects of widening the viewing angle and speeding up the reaction of liquid crystal molecules, thereby solving the problems of inevitable light transmittance and insufficient contrast of the multi-domain vertical alignment type liquid crystal display panel.

In order to polymerize a polymerizable compound, a large amount of ultraviolet light, such as 100,000 J / m ² , must be irradiated. Therefore, in addition to the possibility of liquid crystal molecules being decomposed, unreacted compounds that are not polymerized by irradiating ultraviolet light also remain in the liquid crystal layer at the same time, forming contamination of impurities. ), Which causes the problem of uneven color (mura) of the liquid crystal display element, and particularly adversely affects the electrical characteristics. In addition, the type of liquid crystal molecules used in the liquid crystal layer must also be limited depending on the polymerizable compound added.

Meanwhile, Non-Patent Document 1 proposes a method of forming a liquid crystal alignment film using a polyfluorene-based liquid crystal alignment agent containing a reactive liquid crystal.

At this stage, with the high definition of liquid crystal display elements and the requirements for reduction of contrast or reduction of afterimages of liquid crystal display elements, it is necessary to increase the voltage maintenance rate when using liquid crystal alignment films or reduce the residual charge when applying DC voltage and It is also gradually important that the characteristics of early relieving the residual charge accumulated by the DC voltage are gradually reduced.

In order to increase the voltage maintenance rate and to reduce the residual image charge accumulated due to DC voltage as early as possible even after prolonged exposure to high temperature, it is known to use polyimide and / or polyimide as the polymer. Liquid crystal alignment agent of a diamine compound used as a raw material of an amino acid and a polyimide (for example, refer to Patent Document 1).

However, in recent years, large-screen and high-definition liquid crystal televisions have been widely used. Among these liquid crystal display elements, compared with the previous display applications that mainly used to display text or still images, they must be used in harsh environments. Fast response speed and high body impedance.

Therefore, how to provide a liquid crystal alignment agent for a liquid crystal alignment film with a fast response speed and a high bulk impedance so that the liquid crystal alignment film formed by the liquid crystal alignment film can have a better display quality when applied to a liquid crystal display element is actually a person skilled in the art. Problems to be solved.

[Patent Literature] [Patent Literature 1] Patent Cooperation Treaty International Publication No. WO2009093704

[Non-Patent Literature] [Non-Patent Literature 1] Y. -J. Lee et. Al. SID 09 DIGEST, p. 666 (2009)

In view of this, the present invention provides a liquid crystal alignment agent for a liquid crystal display element. The liquid crystal alignment film prepared by using the liquid crystal alignment agent can improve the problems of poor response speed and poor body impedance.

The invention provides a liquid crystal alignment agent, which includes a polymer (A), a photo-alignable polysiloxane (B), and a solvent (C). The polymer (A) is prepared by reacting a first mixture, and the first mixture includes a tetracarboxylic dianhydride component (a1) and a diamine component (a2). The photo-alignable polysiloxane (B) is obtained by reacting an epoxy-containing polysiloxane (b1), a cinnamic acid derivative (b2), and an ethylenically unsaturated compound (b3).

In one embodiment of the present invention, the epoxy group-containing polysiloxane (b1) includes a group represented by formula (b1-1), a group represented by formula (b1-2), and a group represented by formula (b1 -3) at least one of the bases represented: Formula (b1-1) In formula (b1-1), B represents an oxygen atom or a single bond; m represents an integer from 1 to 3; n represents an integer from 0 to 6, wherein when n represents 0, B is a single bond; * Indicates a bond. Formula (b1-2) In formula (b1-2), p represents an integer of 0 to 6; * represents a bond. Formula (b1-3) In formula (b1-3), D represents an alkylene group having 2 to 6 carbon atoms; E represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; * represents a bond.

In one embodiment of the present invention, the epoxy group-containing polysiloxane (b1) includes a copolymer obtained by hydrolyzing and partially condensing the second mixture. The second mixture includes an epoxy-containing silane compound (b1-1), and the epoxy-containing silane compound (b1-1) has a structure represented by the formula (b1-4): Si (R _x ) _w (OR _y ) _4-w Formula (b1-4) In Formula (b1-4), R _x represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 6 to 6 carbon atoms. 15 aryl group, epoxy-containing alkyl group or epoxy-containing alkoxy group, and at least one R _x is epoxy-containing alkyl group or epoxy-containing alkoxy group; when w is 2 or more when, w a R _x are the same or different. R _y represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms; when w is 2 or less, (4-w) R _y are each the same or different; w represents an integer of 1 to 3.

In an embodiment of the present invention, the cinnamic acid derivative (b2) is selected from at least one of the group consisting of compounds represented by formula (b2-1) and formula (b2-2): Formula (b2-1) Formula (b2-2) In formula (b2-1) and formula (b2-2), R represents a fluorine atom or a cyano group; and a represents an integer of 0 to 4. R ¹ and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 40 carbon atoms or a monovalent alicyclic organic group having 3 to 40 carbon atoms, and a part or all of the hydrogen atom of the alkyl group may be a fluorine atom To replace. R ² and R ⁴ each independently represent a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused cyclic group, and R ² or R ⁴ is unsubstituted or At least a part of the hydrogen atoms are substituted by R ⁸ , and each of R ⁸ independently represents a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, the above-mentioned alkyl group or An alkoxy group is unsubstituted or at least a part of a hydrogen atom is substituted with a halogen. Y ¹ , Y ² , and Y ⁴ each independently represent a single bond, an oxygen atom, -COO-, or -OCO-. Y ⁵ represents a single bond, an alkylene group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a divalent aromatic group. When Y ⁵ represents a single bond, e represents 1, and R ⁵ represents a hydrogen atom; when Y ⁵ represents an alkylene group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a divalent aromatic group In the group, e represents 0 or 1, and R ⁵ represents a carboxylic acid group, a hydroxyl group, -SH, -NCO, -NHR ^' , -CH = CH ₂ or -SO ₂ Cl, and R ^' represents a hydrogen atom or a carbon number of 1. To 6 alkyl. Y ³ represents an oxygen atom or a divalent aromatic group. R ⁶ represents a divalent aromatic group, a divalent heterocyclic group, or a divalent fused ring group. Y ⁶ represents an oxygen atom, -COO-, or -OCO-. R ⁷ represents a carboxylic acid group, a hydroxyl ^{group, -SH, -NCO, -NHR ''} , -CH = CH 2 or -SO ₂ Cl, R ^'' represents a hydrogen atom or an alkyl having 1 to 6. Y ⁷ represents a single bond, -OCO- (CH ₂ ) _i- * or -O- (CH ₂ ) _j- *, where i and j each independently represent an integer from 1 to 10, and * each independently represents an integer from R ⁷ Knot. b, c, and f each independently represent an integer of 0 to 3.

In one embodiment of the present invention, the ethylenically unsaturated compound (b3) has a structure represented by formula (b3-1): In formula (b3-1) of formula (b3-1), R ¹⁰ is an alkylene group having a carbon number linear or branched chain of 1 to 10, phenylene or cyclohexylene, R ¹⁰ is part of hydrogen atoms is substituted Or not replaced. R ¹¹ is a linear or branched alkylene group having a carbon number of 1 to 10, and a part of the hydrogen atom of R ¹¹ is substituted or unsubstituted. R ¹² is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, and a part of the hydrogen atom of R ¹² is substituted or unsubstituted. R ¹³ is a hydrogen atom or a methyl group; L is -OCO-, -O-, or -S-. h is an integer from 0 to 10; k is 0 or 1; when K is 0, h is not 0; when h is 2 or more, h R ¹¹ and L are each the same or different.

In one embodiment of the present invention, the diamine component (a2) includes a diamine compound (a2-1). The diamine compound (a2-1) is at least one selected from the group consisting of compounds represented by formula (a2-1-1), formula (a2-1-2), and formula (a2-1-3): Formula (a2-1-1) Formula (a2-1-2) Formula (a2-1-3) In formulas (a2-1-1) to (a2-1-3), X represents a single bond, -COO-, -CONR _d -or -R _e -NR _d- ; R _a is a single bond or a linear or branched alkyl group having 1 to 10 carbons; R _b is a linear or branched alkoxy, nitrile, or carbonyl group having 1 to 10 carbons; R _c is a carbon number of A linear or branched alkyl group of 1 to 10; or R _b and R _c are combined with each other to form a monocyclic ring. R _d is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbons; R _e is a single bond or a linear or branched alkyl group having 1 to 10 carbons. a1 is 0 or 1; a2 is an integer from 0 to 2; a1 is 0 when X is a single bond; a1 is 1 when X is -COO-, -CONR _d -or -NR _d- .

In one embodiment of the present invention, the diamine component (a2) includes a diamine compound (a2-2) having a fluorenyl group.

In an embodiment of the present invention, based on the above-mentioned second mixture, the total mole number is 1.0 mole, and the amount of the epoxy-containing silane compound (b1-1) used is 0.6 to 1.0 mole.

In an embodiment of the present invention, based on the above-mentioned second mixture, the total mole number is 1.0 mole, the amount of cinnamic acid derivative (b2) used is 0.05 to 0.4 mole, and the ethylenically unsaturated compound (b3) The amount used is 0.1 to 0.4 moles.

In one embodiment of the present invention, the total mole number of the diamine component (a2) is 1.0 mole, and the amount of the diamine compound (a2-1) is 0.2 to 0.6 mole.

In an embodiment of the present invention, the total mole number of the diamine component (a2) is 1.0 mole, and the amount of the diamine compound (a2-2) having a fluorenyl group is 0.2 to 0.6 mole. .

In an embodiment of the present invention, based on the amount of the polymer (A) used above being 100 parts by weight, the amount of the photo-alignable polysiloxane (B) used is 5 to 30 parts by weight; The amount used is 1500 to 4000 parts by weight.

The invention further provides a method for manufacturing a liquid crystal alignment film, comprising the step of applying the liquid crystal alignment agent as described above on a substrate.

The present invention further provides a liquid crystal display element, including: a liquid crystal alignment film prepared by the above-mentioned method for manufacturing a liquid crystal alignment film.

Based on the above, the liquid crystal alignment agent of the present invention can form a liquid crystal alignment film having a fast response speed and a high bulk resistance because it has a specific photo-alignment polysiloxane (B).

In order to make the above features and advantages of the present invention more comprehensible, embodiments are hereinafter described in detail with reference to the accompanying drawings.

< Liquid crystal alignment agent > The present invention provides a liquid crystal alignment agent including a polymer (A), a photo-alignable polysiloxane (B), and a solvent (C). In addition, if necessary, the liquid crystal alignment agent may further include an additive (D).

Hereinafter, each component of the liquid crystal alignment agent used in the present invention will be described in detail. Polymer ( A )

The polymer (A) is obtained by reacting a first mixture, which includes a tetracarboxylic dianhydride component (a1) and a diamine component (a2).

Specifically, the polymer (A) is selected from the group consisting of a polyamidopolymer, a polyamidopolymer, a polyamidoblock copolymer, or any combination thereof. Among them, the polyfluorene-based block copolymer includes a polyfluoride-based block copolymer, a polyfluoride-based imide block copolymer, a polyfluoride-based polyimide-block copolymer, or the above-mentioned polymerization. Combination of things.

Specifically, the polymer (A) includes a unit represented by the formula (a2-1 '): Formula (a2-1 ') In formula (a2-1'), X represents a single bond, -COO-, -CONR _d -or -R _e -NR _d- ; R _a is a single bond or carbon number is 1 to 10 R _b is a straight or branched alkoxy, nitrile or carbonyl group having 1 to 10 carbon atoms; R _c is a straight or branched alkyl group having 1 to 10 carbon atoms Or R _b and R _c may be combined with each other to form a single ring; Ht represents a nitrogen-containing heterocyclic ring; * represents a bond. R _d is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbons; R _e is a single bond or a linear or branched alkyl group having 1 to 10 carbons. a1 is 0 or 1; a2 is an integer from 0 to 2; a1 is 0 when X is a single bond; a1 is 1 when X is -COO-, -CONR _d -or -NR _d- .

More specifically, the polymer (A) includes at least one selected from the units represented by the formula (a2-1'-1) to the formula (a2-1'-3): (A2-1'-1) (A2-1'-2) Formula (a2-1'-3) In formulas (a2-1'-1) to (a2-1'-3), X represents a single bond, -COO-, -CONR _d -or -R _e -NR _d -; R _a is a single bond or a linear or branched alkyl group having 1 to 10 carbons; R _b is a linear or branched alkoxy group, nitrile group, or carbonyl group having 1 to 10 carbon numbers; R _c is A linear or branched alkyl group having 1 to 10 carbons; or R _b and R _c are combined with each other to form a monocyclic ring. R _d is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbons; R _e is a single bond or a linear or branched alkyl group having 1 to 10 carbons. a1 is 0 or 1; a2 is an integer from 0 to 2; when X is a single bond, a1 is 0; when X is -COO-, -CONR _d -or -NR _d- , a1 is 1; * indicates a bond Results.

The polyfluorinated acid polymer, the polyfluorinated imine polymer, and the polyfluorinated block copolymer in the polymer (A) may be each composed of a tetracarboxylic dianhydride component (a1) and a diamine component (a2). ), Which is prepared by the reaction of the mixture, wherein the tetracarboxylic dianhydride component (a1), the diamine component (a2), and the method for manufacturing the polymer (A) are described below. Tetracarboxylic dianhydride component ( a1 )

The tetracarboxylic dianhydride component (a1) includes an aliphatic tetracarboxylic dianhydride compound, an alicyclic tetracarboxylic dianhydride compound, an aromatic tetracarboxylic dianhydride compound, and the formula (a1-1) to (a1) -6) At least one of the tetracarboxylic dianhydride compounds represented by the above, or a combination thereof.

Specific examples of the aliphatic tetracarboxylic dianhydride compound, the alicyclic tetracarboxylic dianhydride compound, and the aromatic tetracarboxylic dianhydride compound are listed below, but the present invention is not limited to these specific examples.

Specific examples of the aliphatic tetracarboxylic dianhydride compound may include, but are not limited to, ethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, or a combination thereof.

Specific examples of the alicyclic tetracarboxylic dianhydride compound may include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclo Butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl Cyclopeptyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, or a combination of the foregoing compounds.

Specific examples of the aromatic tetracarboxylic dianhydride compound may include, but are not limited to, 3,4-dicarboxyl-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylpyrenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-4,4'-diphenylethanetetracarboxylic dianhydride, 3,3 ', 4,4'- Dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4, 4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylarsine dianhydride, 4,4'- Bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride (4,4'-bis (3,4-dicarboxy phenoxy) diphenylpropane dianhydride), 3,3 ', 4,4'-perfluoroisoprene Propyldiphthalic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (tris) Phenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, (Triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitic acid ester), propylene glycol-bis (anhydrotrimellitic acid ester), 1,4 -Butanediol-bis (dehydrated trimellitate), 1,6-hexanediol-bis (dehydrated trimellitate), 1,8-octanediol-bis (dehydrated trimellitate) , 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5, 9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione (1,3,3a , 4,5,9b- hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione), 1,3,3a, 4,5 , 9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione , 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro-2,5-dioxo-3-furyl) -naphtho [1,2-c ] -Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro-2,5 -Dioxo-3-furyl) -naphtho [1,2-c] -furan-1 , 3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro-2,5-dioxo -3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 -(Tetrahydro-2,5-dioxo-3-furyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxo Tetrahydrofuranyl) An aromatic tetracarboxylic dianhydride compound such as 3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride or a combination thereof.

The tetracarboxylic dianhydride compounds represented by the formula (a1-1) to the formula (a1-6) are shown below. (A1-1) (A1-2) (A1-3) (A1-4) Formula (a1-5) In formula (a1-5), A ₁ represents a divalent group containing an aromatic ring; r represents an integer of 1 to 2; A ₂ and A ₃ may be the same or different, and may be independently represented by each other -H or alkyl. Specific examples of the tetracarboxylic dianhydride compound represented by the formula (a1-5) include at least one of compounds represented by the formula (a1-5-1) to the formula (a1-5-3). Formula (a1-5-1) Formula (a1-5-2) Formula (a1-5-3) Formula (a1-6) In formula (a1-6), A ₄ represents a divalent group containing an aromatic ring; A ₅ and A ₆ may be the same or different, and each independently represents -H or an alkyl group. The tetracarboxylic dianhydride compound represented by the formula (a1-6) is preferably a compound represented by the formula (a1-6-1). Formula (a1-6-1)

Preferably, the tetracarboxylic dianhydride component (a1) includes, but is not limited to, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride Anhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetracarboxylic acid Hydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyl Perylene tetracarboxylic dianhydride and a compound represented by formula (a1-1). The tetracarboxylic dianhydride component (a1) can be used alone or in combination.

Based on the total mole number of the diamine component (a2) is 1.0 mole, and the amount of the tetracarboxylic dianhydride component (a1) used is preferably 0.8 to 1.2 moles, and more preferably 0.85 to 1.15 moles. Diamine component ( a2 )

The diamine component (a2) may be selected from at least one of the diamine compound (a2-1) and the diamine compound (a2-2) having a fluorenyl group, and the diamine component (a2) may further include other diamine compounds (A2-3). Diamine compound ( a2-1 )

The diamine compound (a2-1) is at least one selected from the group consisting of compounds represented by formula (a2-1-1), formula (a2-1-2), and formula (a2-1-3): Formula (a2-1-1) Formula (a2-1-2) Formula (a2-1-3) In formula (a2-1-1) to formula (a2-1-3), X represents a single bond, -COO-, -CONR _d -or -R _e -NR _d- . R _a is a single bond or a linear or branched alkyl group having 1 to 10 carbons; R _b is a linear or branched alkoxy group, nitrile group, or carbonyl group having 1 to 10 carbon numbers; R _c is a carbon number A linear or branched alkyl group of 1 to 10; or R _b and R _c combine with each other to form a monocyclic ring. R _d is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbons; R _e is a single bond or a linear or branched alkyl group having 1 to 10 carbons. a1 is 0 or 1; a2 is an integer from 0 to 2; a1 is 0 when X is a single bond; a1 is 1 when X is -COO-, -CONR _d -or -NR _d- .

More specifically, specific examples of the diamine compound (a2-1) include diamine compounds represented by the following formulae (a2-1-4) to (a2-1-23): Formula (a2-1-4) Formula (a2-1-5) Formula (a2-1-6) Formula (a2-1-7) Formula (a2-1-8) Formula (a2-1-9) Formula (a2-1-10) Formula (a2-1-11) Formula (a2-1-12) Formula (a2-1-13) (A2-1-14) Formula (a2-1-15) (A2-1-16) (A2-1-17) (A2-1-18) (A2-1-19) Formula (a2-1-20) Formula (a2-1-21) (A2-1-22) (A2-1-23)

The diamine compound (a2-1) can be used alone or in combination. When the diamine component (a2) of the polymer (A) in the liquid crystal alignment agent contains the diamine compound (a2-1), the bulk impedance of the liquid crystal alignment film can be further increased.

The total mole number based on the diamine component (a2) is 1.0 mole, and the amount of the diamine compound (a2-1) used is 0.2 to 0.6 mole, preferably 0.25 to 0.55 mole, and more preferably 0.25 to 0.5 mole. Diamine compound having a fluorenyl group ( a2-2 )

The diamine compound (a2-2) having a fluorenyl group is a compound having a 9,9-bis (aminophenyl) fluorenyl structure. Specifically, the diamine compound (a2-2) having a fluorenyl group has a structure of the following formula (a2-2): Formula (a2-2) In formula (a2-2), R _m and R _n each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. Further, in the formula (a2-2), a hydrogen atom on a phenyl group or a fluorenyl group may be substituted with a substituent selected from any of the following groups: a halogen atom, an alkyl group, an aryl group, and an alkoxy group , Aryloxy, nitro, ethylfluorenyl, and trimethylsilyl. Preferably, it does not have a substituent.

Specific examples of the diamine compound (a2-2) having a fluorenyl group include 9,9-bis (4-aminophenyl) fluorene and 4-methyl-9,9-bis (4-aminophenylphenyl) ) Fluorene, 4-chloro-9,9-bis (4-aminophenyl) fluorene, 2-ethyl-9,9-bis (4-aminophenyl) fluorene, 2-iodo-9,9- Bis (4-aminophenyl) fluorene, 3-bromo-9,9-bis (4-aminophenyl) fluorene, 9- (4-methylaminophenyl) -9- (4-ethyl Aminophenyl) fluorene, 1-chloro-9,9-bis (4-aminophenyl) fluorene, 2-methyl-9,9-bis (4-aminophenyl) fluorene, 2-fluoro- 9,9-bis (4-aminophenyl) fluorene, 1,2,3,4,5,6,7,8-octafluoro-9,9-bis (4-aminophenyl) fluorene, 2 , 7-dinitro-9,9-bis (4-aminophenyl) fluorene, 2-chloro-4-methyl-9,9-bis (4-aminophenyl) fluorene, 2,7- Dichloro-9,9-bis (4-aminophenyl) fluorene, 2-ethylfluorenyl-9,9-bis (4-aminophenyl) fluorene, 2-chloro-9,9-bis (4 -Aminophenyl) fluorene, 2-third-butyl-9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-methylaminophenyl) fluorene, 9- ( 4-methylaminophenyl) -9- (4-aminophenyl) fluorene, 9,9-bis (4-ethylaminophenyl) fluorene, 9- (4-ethylaminophenyl) ) -9- (4-aminophenyl) fluorene, 9,9-bis (4-n-propylaminophenyl) fluorene, 9,9-bis (4-isopropylaminophenyl) fluorene, 9,9-double (4-n Aminophenyl) fluorene, 9,9-bis (3-methyl-4-methylaminophenyl) fluorene, 9,9-bis (3-chloro-4-methylaminophenyl) fluorene, 9,9-bis (3,5-dimethyl-4-methylaminophenyl) fluorene, 9- (3,5-dimethyl-4-methylaminophenyl) -9- (4 -Methylaminophenyl) fluorene, 1,5-dimethyl-9,9-bis (3,5-dimethyl-4-methylaminophenyl) fluorene, 4-methyl-9, 9-bis (4-methylaminophenyl) fluorene, 4-chloro-9,9-bis (4-methylaminophenyl) fluorene, and 9,9-bis (3,5-diethyl- 4-methylaminophenyl) fluorene. Compounds in which R _m and R _n in the formula (a2-2) each independently represent a hydrogen atom are preferred, such as 9,9-bis (4-aminophenyl) fluorene and 9,9-bis (3-methyl 4-Aminophenyl) fluorene, 9,9-bis (3-ethyl-4-aminophenyl) fluorene, 9,9-bis (3-phenyl-4-aminophenyl) fluorene, 9,9-bis (3,5-dimethyl-4-aminophenyl) fluorene, 9- (3,5-diethyl-4-aminophenyl) -9- (3-methyl- 4-aminophenyl) fluorene, 9- (3-methyl-4-aminophenyl) -9- (3-chloro-4-aminophenyl) fluorene, 9,9-bis (3,5 -Diisopropyl-4-aminophenyl) fluorene and 9,9-bis (3-chloro-4-aminophenyl) fluorene.

The diamine compound (a2-2) which has a fluorenyl group can be used individually or in combination of multiple types. When the diamine component (a2) of the polymer (A) in the liquid crystal alignment agent contains the diamine compound (a2-2) having a fluorene group, the bulk impedance of the liquid crystal alignment film can be further increased.

The total mole number based on the diamine component (a2) is 1.0 mole, and the amount of the diamine compound (a2-2) having a fluorenyl group is 0.2 to 0.6 mole, preferably 0.20 to 0.55 mole, more Preferably it is 0.25 to 0.55 moles. Other diamine compounds ( a2-3 )

Other diamine compounds (a2-3) include aliphatic diamine compounds, alicyclic diamine compounds, aromatic diamine compounds, and diamines having the formula (a2-3-1) to (a2-3-26) A compound, or a combination thereof.

Specific examples of the aliphatic diamine compound include, but are not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane , 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane , 4,4'-diaminoheptane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7 -Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1, 9-diamino-5-methylnonane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis (3-aminopropoxy) ethyl Alkane, or a combination of the above.

Specific examples of the alicyclic diamine compound include, but are not limited to, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 1, 3-diaminocyclohexane, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, tricyclo [6.2.1.0 ^2,7 ] -unda Carbenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine), or a combination thereof.

Specific examples of the aromatic diamine compound include, but are not limited to, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl Hydrazone, 4,4'-diaminobenzidineaniline, 4,4'-diaminostilbene stilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminediamine Phenyl ether, 3,3'-diaminochalcone, 1,5-diaminonaphthalene, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethyl Indanes, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylhydroindene, hexahydro-4,7-methyl bridged indenyldimethylene Diamine, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenylphenyl) ) Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] fluorene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4 -Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 9,10-bis ( 4-aminophenyl) anthracene [9,10-bis (4-aminophenyl) anthracene ], 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 4,4 '-(p -Phenylene isopropylidene) bisaniline, 4,4 '-(m-phenylene isopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoro Methylphenoxy) phenyl] hexafluoropropane, 4,4'bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 5- [4- (4- N-pentylcyclohexyl) cyclohexyl] phenyl-methylene-1,3-diaminobenzene {5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diamino benzene}, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane {1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane}, or a combination thereof.

The diamine compounds having the formula (a2-3-1) to (a2-3-26) are shown below. Formula (a2-3-1) In formula (a2-3-1), G ¹ represents , , , , ,or G ² represents a group having a steroid (cholesterol) skeleton, a trifluoromethyl group, a fluoro group, an alkyl group having 2 to 30 carbon atoms, or derived from pyridine, pyrimidine, triazine, piperidine, or piperazine, etc. A monovalent group containing a nitrogen atom ring structure.

Specific examples of the compound represented by formula (a2-3-1) include, but are not limited to, 2,4-diaminophenyl ethyl formate, 3,5-diaminophenyl Ethyl 3,5-diaminophenyl ethyl formate, 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate, 5-diaminophenyl propyl formate), 1-dodecoxy-2,4-diaminobenzene, 1-dodecoxy-2,4-diaminobenzene Benzene (1-hexadecoxy-2,4-diaminobenzene), 1-octadecoxy-2,4-diaminobenzene (1-octadecoxy-2,4-diaminobenzene), by the formula (a2-3-1- 1) At least one of the compounds represented by the formula (a2-3-1-6), or a combination of the aforementioned compounds.

The compounds represented by the formula (a2-3-1-1) to the formula (a2-3-1-6) are shown below. (A2-3-1-1) (A2-3-1-2) (A2-3-1-3) (A2-3-1-4) (A2-3-1-5) (A2-3-1-6)

In formula (a2-3-2) of formula (a2-3-2), G ¹ in formula (a2-3-1) G same as ^1, G ³ and G ⁴ each independently represents a divalent aliphatic ring, two Valent aromatic ring or divalent heterocyclic group; G ⁵ represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, and a carbon number of 1 to 5 fluoroalkoxy, cyano or halogen atoms.

Specific examples of the compound represented by the formula (a2-3-2) include at least one of compounds represented by the following formula (a2-3-2-1) to the formula (a2-3-2-13): Formula (a2-3-2-1) Formula (a2-3-2-2) (A2-3-2-3) (A2-3-2-4) Formula (a2-3-2-5) Formula (a2-3-2-6) Formula (a2-3-2-7) Formula (a2-3-2-8) Formula (a2-3-2-9) Formula (a2-3-2-10) Formula (a2-3-2-11) Formula (a2-3-2-12) Formula (a2-3-2-13) In formula (a2-3-2-1) to formula (a2-3-2-13), s represents an integer of 3 to 12.

Formula (a2-3-3) In formula (a2-3-3), G ⁶ each independently represents a hydrogen atom, a fluorenyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, and a carbon number of 1 To 5 alkoxy or halogen atoms, and G ⁶ in each repeating unit may be the same or different; i represents an integer of 1 to 3.

Specific examples of the compound represented by the formula (a2-3-3) include when i is 1: p-diaminebenzene, m-diaminebenzene, o-diaminebenzene, 2,5-diaminotoluene, and the like; When i is 2: 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4 ' -Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3 '-Dichloro-4,4'-diaminobiphenyl, 2,2', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4, 4'-diamino-5,5'-dimethoxybiphenyl or 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, etc .; or when i is 3 : 1,4-bis (4'-aminophenyl) benzene and the like.

Specific examples of the compound represented by the formula (a2-3-3) include preferably p-diaminebenzene, 2,5-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'- Dimethoxy-4,4'-diaminobiphenyl, 1,4-bis (4'-aminophenyl) benzene or a combination thereof.

Formula (a2-3-4) In formula (a2-2-4), v represents an integer of 2-12.

Formula (a2-3-5) In formula (a2-3-5), u represents an integer of 1 to 5. The compound represented by the formula (a2-3-5) is preferably 4,4'-diamino-diphenylsulfide.

Formula (a2-3-6) In formula (a2-3-6), G ⁷ and G ⁹ each independently represent a divalent organic group, and G ⁷ and G ⁹ may be the same or different; G ⁸ represents a derivative derived from pyridine , A divalent group having a cyclic structure containing a nitrogen atom such as pyrimidine, triazine, piperidine, or piperazine.

In formula (a2-3-7) of formula ^{(a2-3-7), G 10, G} 11, G 12 and G ¹³ are each independently a hydrocarbon group having a carbon number of 1 to 12, and G ^10, G ^11, G ¹² And G ¹³ may be the same or different; x1 each independently represents an integer of 1 to 3; x2 represents an integer of 1 to 20.

Formula (a2-3-8) In formula (a2-3-8), G ¹⁴ represents an oxygen atom or a cyclohexane group; G ¹⁵ represents a methylene group; G ¹⁶ represents a phenyl group or a cyclohexane group; G ¹⁷ represents a hydrogen atom or a heptyl group.

Specific examples of the compound represented by the formula (a2-3-8) include a compound represented by the formula (a2-3-8-1), a compound represented by the formula (a2-3-8-2), or a combination thereof : Formula (a2-3-8-1) (A2-3-8-2)

The compounds represented by the formula (a2-3-9) to the formula (a2-3-25) are shown below. (A2-3-9) (A2-3-10) (A2-3-11) (A2-3-12) (A2-3-13) (A2-3-14) (A2-3-15) (A2-3-16) (A2-3-17) (A2-3-18) (A2-3-19) (A2-3-20) (A2-3-21) (A2-3-22) (A2-3-23) (A2-3-24) Formula (a2-3-25) In formulas (a2-3-17) to (a2-3-25), G ^{18 is} preferably an alkyl group having 1 to 10 carbon atoms or 1 to 10 carbon atoms. Alkoxy; G ¹⁹ preferably represents a hydrogen atom, an alkyl group having 1 to 10 carbons, or an alkoxy group having 1 to 10 carbons.

Formula (a2-3-26) In formula (a2-3-26), G ²⁰ and G ²² independently represent a single bond, -O-, -COO-, or -OCO-; G ²¹ is a carbon number of 1 to 3 G ²³ is a single bond or an alkylene group having 1 to 3 carbon atoms. j and g each independently represent 0 or 1; l represents an integer from 0 to 2; t represents an integer from 1 to 20; wherein q and u are not 0 at the same time.

In the formula (a2-3-26), with ^{"-G 20 - (G 21 -G 22} ) j - " represents a divalent group is preferably an alkylene group having a carbon number of 1 to 3, * - O- , * -COO- or * -OC ₂ H ₄ -O- (where * represents a bonding point to a diaminophenyl group.). The group represented by "-C _t H _{2t + 1} " is preferably linear. The positions of two amine groups in the diaminophenyl group with respect to other groups are preferably the 2, 4-position or the 3, 5-position.

Specific examples of the compound represented by the formula (a2-3-26) include compounds represented by the following formula (a2-3-26-1) to (a2-3-26-4): (A2-3-26-1) (A2-3-26-2) (A2-3-26-3) (A2-3-26-4)

The other diamine compounds (a2-3) can be used alone or in combination.

Specific examples of the other diamine compound (a2-3) preferably include, but are not limited to, 1,2-diaminoethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamine Diphenylmethane, 4,4'-diaminodiphenyl ether, 5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diaminobenzene , 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane, 2,4-diaminophenylethyl formate, 1 -Octadecyloxy-2,4-diaminobenzene, a compound represented by formula (a2-3-1-1), a compound represented by formula (a2-3-1-2), A compound represented by -3-2-1), a compound represented by formula (a2-3-2-11), p-diaminebenzene, m-diaminebenzene, o-diaminebenzene, -8-1) or a combination thereof.

The mole number based on the diamine component (a2) is 1.0 mole, and the amount of the other diamine compound (a2-3) used is 0.2 to 1.0 mole, preferably 0.3 to 1.0 mole, and more preferably 0.4 to 1.0 mole. Method for manufacturing polymer ( A )

The polymer (A) may include at least one of a polyamidic acid and a polyimide. The polymer (A) may further include a polyfluorene-based block copolymer. Hereinafter, the manufacturing method of the said various polymers is demonstrated further. Method for producing polyamic acid

The method for manufacturing polyamic acid is to first dissolve a first mixture in a solvent, wherein the first mixture includes a tetracarboxylic dianhydride component (a1) and a diamine component (a2), and the temperature is from 0 ° C to 100 ° C. The polycondensation reaction proceeds at a temperature. After reacting for 1 hour to 24 hours, the reaction solution is distilled under reduced pressure using an evaporator to obtain polyamic acid. Alternatively, the reaction solution is poured into a large amount of a lean solvent to obtain a precipitate. Then, the precipitate is dried under reduced pressure to obtain polyamic acid.

The solvent used in the polycondensation reaction may be the same as or different from the solvent in the liquid crystal alignment agent described below, and the solvent used in the polycondensation reaction is not particularly limited as long as it can dissolve the reactant and the product. The solvent preferably includes, but is not limited to (1) an aprotic polar solvent, such as: N-methyl-2-pyrrolidinone (NMP), N, N-dimethylacetamide, Aprotic polar solvents such as N, N-dimethylformamide, dimethylmethylene sulfoxide, γ-butyrolactone, tetramethylurea or hexamethyl phosphate triamine; or (2) phenolic solvents, For example: m-cresol, xylenol, phenol or halogenated phenols. The use amount of the solvent used in the polycondensation reaction is preferably 200 parts by weight to 2000 parts by weight, and more preferably 300 parts by weight to 1800 parts by weight based on the total use amount of the first mixture.

It is worth noting that in the polycondensation reaction, an appropriate amount of a lean solvent can be used in combination with the solvent, wherein the lean solvent does not cause the polyamic acid to precipitate. The lean solvent can be used singly or in combination, and it includes but is not limited to (1) alcohols, such as: methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butane Alcohols or alcohols such as triethylene glycol; (2) ketones, such as: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; (3) esters, such as: Esters such as methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, or ethylene glycol ethyl ether acetate; (4) ethers, such as diethyl ether, Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, or diethylene glycol dimethyl ether Ethers such as alkyl ethers; (5) halogenated hydrocarbons, such as: dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, or o-dichloro Halogenated hydrocarbons such as benzene; or (6) hydrocarbons, for example: hydrocarbons such as tetrahydrofuran, hexane, heptane, octane, benzene, toluene or xylene, or any combination of the above solvents. Based on the used amount of the diamine component (b) being 100 parts by weight, the amount of the lean solvent is preferably 0 to 60 parts by weight, and more preferably 0 to 50 parts by weight. Method for manufacturing polyfluorene

The method for producing polyimide is obtained by heating the polyamic acid produced by the method for producing a polyamic acid in the presence of a dehydrating agent and a catalyst. During the heating process, the arsenic acid functional group in the polyarsenic acid can be converted into the arsonimine functional group (that is, arsonimation) through a dehydration ring-closing reaction.

The solvent used in the dehydration ring-closing reaction may be the same as the solvent (C) in the liquid crystal alignment agent, so it will not be repeated here. The amount of the solvent used in the dehydration ring-closing reaction is preferably 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight, based on 100 parts by weight of the polyamic acid used.

In order to obtain a better degree of polyimidation of the polyimide, the operating temperature of the dehydration ring-closing reaction is preferably 40 ° C to 200 ° C, and more preferably 40 ° C to 150 ° C. If the operating temperature of the dehydration ring-closing reaction is lower than 40 ° C, the imidization reaction is not complete, and the degree of imidization of the polyacid is reduced. However, if the operating temperature of the dehydration ring-closing reaction is higher than 200 ° C, the weight average molecular weight of the obtained polyfluorene imine is low.

The dehydrating agent used in the dehydration ring-closure reaction may be selected from acid anhydride compounds, and specific examples thereof include acid anhydride compounds such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. Based on 1 mole of polyamic acid, the amount of dehydrating agent used is 0.01 to 20 moles. The catalyst used in the dehydration ring-closing reaction may be selected from (1) pyridine compounds, such as pyridine, trimethylpyridine, or dimethylpyridine; and (2) tertiary amine compounds, such as: Tertiary amines such as triethylamine. Based on the amount of dehydrating agent used is 1 mole, the amount of catalyst used can be 0.5 to 10 moles.

The amidation ratio of the polymer (A) may be 0% to 50%, preferably 0% to 45%, and more preferably 0% to 40%. Method for manufacturing polyfluorene-based block copolymer

The polyimide-based block copolymer is selected from the group consisting of a polyimide block copolymer, a polyimide block copolymer, a polyimide-polyimide block copolymer, or the above-mentioned polymerization. Any combination of things.

The method for manufacturing a polyfluorene-based block copolymer is preferably firstly dissolving a starting material in a solvent and carrying out a polycondensation reaction, wherein the starting material includes at least one polyamic acid and / or at least one polyfluorene Imine, and may further include a carboxylic anhydride component and a diamine component.

The carboxylic acid anhydride component and the diamine component in the starting material may be the same as the tetracarboxylic dianhydride component (a1) and the diamine component (a2) used in the method for producing a polyamic acid, and are used for The solvent in the polycondensation reaction may be the same as the solvent (C) in the liquid crystal alignment agent described below, and will not be repeated here.

The used amount of the solvent used in the polycondensation reaction is preferably 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight based on the used amount of the starting material. The operating temperature of the polycondensation reaction is preferably 0 ° C to 200 ° C, and more preferably 0 ° C to 100 ° C.

The starting materials preferably include, but are not limited to, (1) two polyamido acids having different terminal groups and different structures; (2) two polyimines having different terminal groups and different structures; (3) ) Polyamines and polyimines having different terminal groups and structures; (4) Polyamines, carboxylic anhydride components, and diamine components, of which the carboxylic anhydride component and the diamine component are At least one of them is different from the structure of the carboxylic acid anhydride component and the diamine component used to form the polyfluorinated acid; (5) the polyfluorene imine, the carboxylic acid anhydride component, and the diamine component, wherein At least one of the component and the diamine component is different from the structure of the carboxylic acid anhydride component and the diamine component used to form the polyimide; (6) the polyamidic acid, the polyimide, and the carboxylic acid anhydride component And a diamine component, wherein at least one of the carboxylic acid anhydride component and the diamine component is different from the structure of the carboxylic acid anhydride component and the diamine component used to form the polyamic acid or polyimide; ( 7) Two kinds of polyfluorinated acid, carboxylic anhydride and diamine components with different structures; (8) Two kinds of polyfluorinated imine, carboxylic anhydride and diamine components with different structures; (9) Polyamines and diamines whose terminal groups are acid anhydride groups and have different structures; (10) Polyamines and carboxylic anhydrides whose terminal groups are amine groups and have different structures; (11) A kind of polyfluorene imine and diamine components whose terminal groups are acid anhydride groups and different structures; or (12) two kinds of polyfluorene imine and carboxylic acid anhydride components whose terminal groups are amine groups and different structures.

As long as the efficacy of the present invention is not affected, the polyamidic acid, polyamidoimide, and polyamidoimide block copolymer are preferably terminally modified polymers after molecular weight adjustment. By using a terminal-modified polymer, the coating performance of the liquid crystal alignment agent can be improved. The method for producing a terminal-modified polymer can be obtained by adding a polyfunctional compound while the polyamic acid undergoes a polycondensation reaction.

Specific examples of monofunctional compounds include, but are not limited to (1) monobasic anhydrides, such as: maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecyl Monobasic anhydrides such as alkyl succinic anhydride or n-hexadecyl succinic anhydride; (2) monoamine compounds such as: aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, N-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecanylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecanylamine, Monoamine compounds such as n-octadecylamine or n-eicosylamine; or (3) monoisocyanate compounds, such as monoisocyanate compounds such as phenyl isocyanate or naphthyl isocyanate.

The polymer (A) of the present invention has a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography method of 10,000 to 100,000, preferably 20,000 to 80,000, and more preferably 30,000 to 70,000. Photo-alignable polysiloxane ( B )

The photo-alignable polysiloxane (B) is obtained by reacting an epoxy-containing polysiloxane (b1), a cinnamic acid derivative (b2), and an ethylenically unsaturated compound (b3). In addition, as long as the effect of the present invention is not impaired, a part of the ethylenically unsaturated compound (b3) may be replaced with a carboxylic acid compound (b4). In this case, the synthesis of the photo-alignable polysiloxane (B) can be achieved by combining an epoxy-containing polysiloxane (b1) with a cinnamic acid derivative (b2) and an ethylenically unsaturated compound (b3) A mixture of carboxylic acid compound (b4) is reacted to proceed. Specific examples and synthesis methods of the epoxy group-containing polysiloxane (b1), cinnamic acid derivative (b2), ethylenically unsaturated compound (b3), and carboxylic acid compound (b4) will be described below. Polysiloxane containing epoxy groups ( b1 )

The epoxy group contained in the epoxy group-containing polysiloxane (b1) is, for example, a glycidyl group, a glycidyloxy group, an epoxycyclohexyl group, or an epoxy group. Oxetanyl group.

Specifically, the epoxy group-containing polysiloxane (b1) includes at least one selected from the group represented by formula (b1-1) to formula (b1-3): Formula (b1-1) In formula (b1-1), B represents an oxygen atom or a single bond; m represents an integer from 1 to 3; n represents an integer from 0 to 6, wherein when n represents 0, B is a single bond; * Indicates a bond. Formula (b1-2) In formula (b1-2), p represents an integer of 0 to 6; * represents a bond. Formula (b1-3) In formula (b1-3), D represents an alkylene group having 2 to 6 carbon atoms; E represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; * represents a bond.

The epoxy group-containing group preferably includes a group represented by the formula (b1-1-1), a group represented by the formula (b1-2-1), and a group represented by the formula (b1-3-1) At least one of them. Formula (b1-1-1) Formula (b1-2-1) Formula (b1-3-1)

The epoxy group-containing polysiloxane (b1) preferably contains a copolymer obtained by subjecting a second mixture to hydrolysis and partial condensation, and the second mixture includes an epoxy group-containing silane compound (b1-1), The epoxy group-containing silane compound (b1-1) has a structure represented by formula (b1-4): Si (R _x ) _w (OR _y ) _4-w formula (b1-4) formula (b1- In 4), R _x represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkyl group containing an epoxy group, or a ring containing a ring An alkoxy group of an oxygen group, and at least one R _x is an alkyl group containing an epoxy group or an alkoxy group containing an epoxy group; when w is 2 or more, w R _x are each the same or different. R _Y represents a hydrogen atom, alkyl having 1 to 6 carbon atoms or acyl of 1 to 6 carbon atoms, an aryl group having 6 to 15; when w is 2 or less, (4-w) R & _y are each the same or different; w represents an integer of 1 to 3.

In the definition of R _x , the epoxy group is the epoxy group contained in the epoxy group-containing polysiloxane (b1), and details are not described herein again.

When R _x in the formula (b1-4) represents an alkyl group having 1 to 10 carbon atoms, specifically, R _x is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, Tributyl, n-hexyl or n-decyl. R _x may be an alkyl group having another substituent on the alkyl group. Specifically, R _{x is,} for example, trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3- Thiopropyl or 3-isocyanatopropyl.

When R _x in the formula (b1-4) represents an alkenyl group having 2 to 10 carbon atoms, specifically, R _{x is,} for example, a vinyl group. R _x may be an alkenyl group having another substituent on the alkenyl group. Specifically, R _{x is,} for example, 3-propenyloxypropyl or 3-methacryloxypropyl.

When R _x in the formula (b1-4) represents an aryl group having 6 to 15 carbon atoms, specifically, R _x is, for example, a phenyl group, a tolyl group, or a naphthyl group. R _x may be an aryl group having another substituent on the aryl group. Specifically, R _x is, for example, p-hydroxyphenyl, 1- (p-hydroxyphenyl) ethyl (1 -(p-hydroxy phenyl) ethyl), 2- (p-hydroxyphenyl) ethyl, or 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl (4-hydroxy-5- (p-hydroxyphenyl carbonyloxy) pentyl).

In the definition of R _y , an alkyl group having 1 to 6 carbon atoms includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like. The fluorenyl group having a carbon number of 1 to 6 includes, but is not limited to, ethynyl. Aryl groups having 6 to 15 carbon atoms include, but are not limited to, phenyl.

Specific examples of the epoxy-containing silane compound (b1-1) include 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, and 3- (N-allyl-N-glycidyl) Group) aminopropyltrimethoxysilane, 3-glycidyletherpropyltrimethoxysilane, 3-glycidyletherpropyltriethoxysilane, 3-glycidyletherpropylmethyldimethyl Oxysilane, 3-glycidyl ether propyl methyl diethoxy silane, 3-glycidyl ether propyl dimethyl methoxy silane, 3-glycidyl ether propyl dimethyl ethoxy Silane, 2-glycidyl ether ethyltrimethoxysilane, 2-glycidyl ether ethyltriethoxysilane, 2-glycidyl ether ethylmethyldimethoxysilane, 2-glycidyl ether Ethyl ethyl methyl diethoxysilane, 2-glycidyl ether ethyl dimethyl methoxysilane, 2-glycidyl ether ethyl dimethyl ethoxysilane, 4-glycidyl ether butyl Trimethoxysilane, 4-glycidyl ether butyltriethoxysilane, 4-glycidyl ether butylmethyldimethoxysilane, 4-glycidyl ether butylmethyldiethoxysilane , 4-glycidyl ether butyldimethylmethoxysilane, 4-glycidyl ether butyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxy Cyclohexyl) propyltriethoxysilane, ((3-ethyl-3-glycidyl) methoxy) propyltrimethoxysilane, ((3-ethyl-3-glycidyl) Methoxy) propyltriethoxysilane, ((3-ethyl-3-glycidyl) methoxy) propylmethyldimethoxysilane, or ((3-ethyl-3-cyclo Oxypropylalkyl) methoxy) propanedimethylmethoxysilane, commercially available products such as DMS-E01, DMS-E12, DMS-E21, EMS-32 (manufactured by JNC), or a combination of these compounds.

Specific examples of the epoxy group-containing silane compound (b1-1) include 3-glycidyl ether propyltrimethoxysilane, 2-glycidyl ether ethyltrimethoxysilane, and 4-glycidyl ether. Butyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, ((3 -Ethyl-3-glycidyl) methoxy) propyltrimethoxysilane, ((3-ethyl-3-glycidyl) methoxy) propyltriethoxysilane, DMS- E01, DMS-E12 or a combination of the above compounds.

The total mole number of the monomer based on the second mixture is 1.0 mole, and the amount of the epoxy-containing silane compound (b1-1) used is 0.6 to 1.0 mole, preferably 0.65 to 1.0 mole, and more preferably It is 0.7 to 1.0 mole. When the epoxy-containing silane compound (b1-1) is not contained in the second mixture, the epoxy-containing polysiloxane (b1) does not contain the epoxy group, and further, the obtained The liquid crystal alignment film formed by the liquid crystal alignment agent has a low bulk impedance and a slow response speed.

Preferably, the second mixture for reacting to form an epoxy group-containing polysiloxane (b1) further comprises another silane compound (b1-2). The other silane compound (b1-2) has a formula (b1-5) ): Si (R _h ) _y (OR _k ) _4-y Formula (b1-5) In formula (b1-5), R _h represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, carbon Alkenyl groups of 2 to 10, aryl groups of 6 to 15 carbons or alkyl groups containing acid anhydride groups; when y is 2 or more, the y _Rhs are the same or different. R _k represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms; when y is 2 or less, (4-y) R _h are each the same or different; y represents an integer from 0 to 3.

The alkyl group containing an acid anhydride group is preferably an alkyl group containing an acid anhydride group and having 1 to 10 carbon atoms, such as, but not limited to, ethyl succinic anhydride, propyl succinic anhydride, propyl glutaric anhydride, and the like. Specifically, the alkyl group containing an acid anhydride group is, for example, ethylsuccinic anhydride represented by formula (b1-5-1), propylsuccinic anhydride represented by formula (b1-5-2), or formula ( b1-5-3) is propylglutaric anhydride. It is worth mentioning that the acid anhydride group is a group formed by dicarboxylic acid by intramolecular dehydration. The dicarboxylic acid is, for example, succinic acid or glutaric acid. Formula (b1-5-1) Formula (b1-5-2) Formula (b1-5-3)

In the definition of R _h , an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and a carbon number having 1 to 10 carbon atoms as defined in the foregoing R _x The alkyl group, the alkenyl group having 2 to 10 carbon atoms, or the aryl group having 6 to 15 carbon atoms are the same, and details are not described herein again.

In the definition of R _k , the alkyl group having 1 to 6 carbons includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like. The fluorenyl group having a carbon number of 1 to 6 includes, but is not limited to, ethynyl. Aryl groups having 6 to 15 carbon atoms include, but are not limited to, phenyl.

The other silane compounds (b1-2) having a structure represented by the formula (b1-5) may be used alone or in combination, and the other silane compounds (b1-2) include a compound having one silicon atom. The compound having one silicon atom includes a silane compound having four hydrolyzable groups, a silane compound having three hydrolyzable groups, a silane compound having two hydrolyzable groups, and a silane having one hydrolyzable group. Compound, or a combination thereof.

Specific examples of the silane compound having four hydrolyzable groups include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane , Tetra-second butoxysilane, or a combination thereof.

Specific examples of the silane compound having three hydrolyzable groups include methyltrimethoxysilane (MTMS), methyltriethoxysilane, and methyltriisopropoxy silane. , Methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxy silane , Ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane, n-butyltrimethoxysilane Silane (n-butyltrimethoxy silane), n-butyl triethoxysilane (n-butyl triethoxysilane), n-hexyltrimethoxysilane (n-hexyltrimethoxysilane), n-hexyltriethoxysilane (n-hexyltriethoxysilane), decyl Decyltrimethoxy silane, vinyl trimethoxysilane, vinyltriethoxysilane, 3-propene trioxide 3-acryoyloxypropyl trimethoxysilane, 3-methylacryloyloxypropyltrimethoxysilane (MPTMS), 3-methacryloxypropyltrimethoxysilane 3-methylacryloyloxypropyl triethoxysilane, phenyltrimethoxysilane (PTMS), phenyltriethoxysilane (PTES), p-hydroxyphenyltrimethoxysilane, 1- (P-hydroxyphenyl) ethyltrimethoxysilane (1- (p-hydroxyphenyl) ethyltrimethoxysilane), 2- (p-hydroxyphenyl) ethyltrimethoxysilane (2- (p-hydroxyphenyl) ethyltrimethoxysilane) 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl trimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl trimethoxysilane, trifluoromethyl trimethoxysilane ), Trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane (3-a minopropyl trimethoxysilane), 3-aminopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3- (triphenoxysilyl) propylbutyl 3-triphenoxy silyl propyl succinic anhydride, a commercially available product manufactured by Shin-Etsu Chemical Co .: 3- (trimethoxysilyl propyl succinic anhydride) (trade name X-12) -967), commercially available products manufactured by WACKER: 3- (triethoxysilyl) propyl succinic anhydride (trade name GF-20), 3- ( 3- (trimethoxysilyl) propyl glutaric anhydride (TMSG), 3- (triethoxysilyl) propyl glutaric anhydride, 3- (triphenoxysilyl) propyl glutaric anhydride or a combination thereof.

Specific examples of the silane compound having two hydrolyzable groups include methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane , Di-n-butyldimethoxysilane, or a combination thereof.

Specific examples of the silane compound having one hydrolyzable group include methoxydimethylsilane, methoxytrimethylsilane, methoxymethyldiphenylsilane, tri-n-butylethoxysilane, or A combination of the above compounds.

The other silane compound (b1-2) having a structure represented by formula (b1-5) is preferably tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane , Phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, thiomethyltrimethoxysilane, thiomethyltriethyl Oxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, or a combination thereof.

The total mole number of the monomer based on the second mixture is 1.0 mole, and the amount of the other silane compound (b1-2) used is 0 to 0.4 mole, preferably 0 to 0.35 mole, and more preferably 0 to 0.3. Mor.

The second mixture may further include a commercially available silane compound, and specific examples thereof include KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X- 22-170D, X-22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40- 2655A, X-40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (made by Shin-Etsu Chemical); glass resin (GLASS RESIN, manufactured by Showa Denko); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (made by Toray Dow Corning); FZ3711, FZ3722 (made by NUC); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS- S32, DMS-S33, DMS-S35 DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (made by JNC); MS51, MS56 (made by Mitsubishi Chemical); and Some condensates of GR100, GR650, GR908, GR950 (manufactured by Showa Denko).

The polycondensation reaction to form the epoxy group-containing polysiloxane (b1) can be performed by a general method, for example, adding an organic solvent, water, or optionally further adding a catalyst to the above-mentioned silane compound or a mixture thereof, and then using an oil A bath or the like is heated at 50 ° C to 150 ° C, and the heating time is preferably 0.5 hours to 120 hours. During heating, the mixed solution may be stirred or placed under reflux conditions.

The organic solvent is not particularly limited, and may be the same as or different from the solvent (C) contained in the liquid crystal alignment agent of the present invention.

Specific examples of the organic solvent include hydrocarbon compounds such as toluene and xylene; methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, diethyl ketone, cyclohexanone, and 2-butanone , 2-hexanone and other ketone solvents; ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and other esters Solvents; Ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc .; 1-hexanol, 4-methyl 2-pentanol, ethylene glycol mono Methyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, etc. Alcohol solvents; N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, trimethylamine hexamethyl phosphate, 1,3-dimethyl Amidamine-based solvents such as 2-imidazolidinone, or a combination of the above organic solvents.

These organic solvents may be used alone or in combination.

The use amount of the organic solvent is preferably 10 to 1200 parts by weight, and more preferably 30 to 1,000 parts by weight, based on 100 parts by weight of all the silane compounds.

The total number of moles of the hydrolyzable groups based on all the silane compounds is 1 mole, and the amount of water used is preferably 0.5 to 5 moles.

The catalyst is not particularly limited. Preferably, the catalyst is selected from the group consisting of an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, or a combination thereof.

Specific examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid, polybasic acid anhydride, or a combination thereof.

Specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, or a combination thereof.

Specific examples of the organic base include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; triethylamine, triethylamine Tertiary organic amines such as n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, etc .; tertiary organic compounds such as tetramethylammonium hydroxide Amines, etc. or a combination of the above.

The amount of catalyst used varies depending on the reaction conditions such as type and temperature, and can be set appropriately. For example, the total mole number of all silane compounds is 1 mole, and the amount of catalyst added is 0.01 mole to 5 moles. , Preferably 0.03 to 3 mol, more preferably 0.05 to 1 mol.

From the viewpoint of stability, after the completion of the polycondensation reaction, the organic solvent layer fractionated from the reaction liquid is preferably washed with water. When washing, washing with water containing a small amount of salts, for example, about 0.2% by weight of an ammonium nitrate aqueous solution or the like is preferred. The washing can be performed until the water layer after the washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the organic solvent is removed to obtain an epoxy group-containing Polysiloxane (b1).

The epoxy-containing polysiloxane (b1) used in the photo-alignable polysiloxane (B) of the present invention includes at least one epoxy-containing polysiloxane (b1) prepared in the following manner. . Specific examples of this method include, but are not limited to, continuous stirring when a catalyst is added in a polycondensation reaction, batch addition of a silane compound during a polycondensation reaction, and the like.

When the epoxy-group-containing polysiloxane (b1) used in the photo-alignment-type polysiloxane (B) does not include an epoxy-group-containing polysiloxane (b1) prepared in the above manner, The liquid crystal alignment film formed by the prepared liquid crystal alignment agent has low bulk impedance and slow response speed. Cinnamic acid derivative ( b2 )

The cinnamic acid derivative (b2) is selected from at least one of the group consisting of compounds represented by formula (b2-1) and formula (b2-2): Formula (b2-1) Formula (b2-2) In formula (b2-1) and formula (b2-2), R represents a fluorine atom or a cyano group; and a represents an integer of 0 to 4. R ¹ and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 40 carbon atoms or a monovalent alicyclic organic group having 3 to 40 carbon atoms, and a part or all of the hydrogen atom of the alkyl group may be a fluorine atom To replace. R ² and R ⁴ each independently represent a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused cyclic group, and R ² or R ⁴ is unsubstituted or At least a part of the hydrogen atoms are substituted by R ⁸ , and each of R ⁸ independently represents a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, the above-mentioned alkyl group or An alkoxy group is unsubstituted or at least a part of a hydrogen atom is substituted with a halogen. Y ¹ , Y ² , and Y ⁴ each independently represent a single bond, an oxygen atom, -COO-, or -OCO-. Y ⁵ represents a single bond, an alkylene group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a divalent aromatic group. When Y ⁵ represents a single bond, e represents 1, and R ⁵ represents a hydrogen atom; when Y ⁵ represents an alkylene group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a divalent aromatic group In the group, e represents 0 or 1, and R ⁵ represents a carboxylic acid group, a hydroxyl group, -SH, -NCO, -NHR ^' , -CH = CH ₂ or -SO ₂ Cl, and R ^' represents a hydrogen atom or a carbon number of 1. To 6 alkyl. Y ³ represents an oxygen atom or a divalent aromatic group. R ⁶ represents a divalent aromatic group, a divalent heterocyclic group, or a divalent fused ring group. Y ⁶ represents an oxygen atom, -COO-, or -OCO-. R ⁷ represents a carboxylic acid group, a hydroxyl ^{group, -SH, -NCO, -NHR ''} , -CH = CH 2 or -SO ₂ Cl, R ^'' represents a hydrogen atom or an alkyl having 1 to 6. Y ⁷ represents a single bond, -OCO- (CH ₂ ) _i- * or -O- (CH ₂ ) _j- *, where i and j each independently represent an integer from 1 to 10, and * each independently represents an integer from R ⁷ Knot. b, c, and f each independently represent an integer of 0 to 3.

It should be noted here that although the cinnamic acid derivatives in the description of the present invention are all represented by the trans (trans) structure, as long as the effect of the present invention is not affected, the cinnamic acid derivatives of the cis (cis) structure are also present in the present invention. Within the scope of the cinnamic acid derivative described in the description of the invention.

In the formulae (b2-1) and (b2-2), the alkyl group having 1 to 40 carbon atoms may be a linear or branched alkylene group, and an alkyl group having 1 to 20 carbon atoms is preferred. , More preferably an alkyl group having 1 to 12 carbons, and particularly preferably an alkyl group having 4 to 12 carbons. A part or all of the hydrogen atom of the alkyl group may be substituted with a fluorine atom, and in this case, a fluorine-containing alkyl group having 3 to 6 carbon atoms is preferred. Specific examples of the alkyl group include the following: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-month Lauryl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl , N-eicosyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,5,5,5-pentafluoropentyl, 4,4,5, 5,6,6,6-heptafluorohexyl, 3,3,4,4,5,5,5-heptafluoropentyl, 2,2,2-trifluoroethyl, 2,2,3,3, 3-pentafluoropropyl, 2- (perfluorobutyl) ethyl, 2- (perfluorooctyl) ethyl, 2- (perfluorodecyl) ethyl and the like.

Examples of the monovalent alicyclic organic group having 3 to 40 carbon atoms in the formulae (b2-1) and (b2-2) include cyclohexylmethyl, cyclohexylpropyl, and cyclohexylpropyl. Cyclohexylpentyl, cyclohexylheptyl, cyclooctyl, lanostyl, cholestenyl, cholestanyl, adamantyl and the like.

Examples of the divalent aromatic group in the formula (b2-1) and the formula (b2-2) include 1,4-phenylene, 2-fluoro-1,4-phenylene, and 3-fluoro-1, 4-phenylene, 2,3,5,6-tetrafluoro-1,4-phenylene and the like.

Examples of the divalent alicyclic group in the formula (b2-1) and the formula (b2-2) include 1,4-cyclohexyl, 2-fluoro-1,4-cyclohexyl, and 3-fluoro-1 , 4-cyclohexyl, 2,3,5,6-tetrafluoro-1,4-cyclohexyl and the like.

Examples of the divalent heterocyclic group in the formula (b2-1) and the formula (b2-2) include 1,4-pyridyl, 2,5-pyridyl, and 1,4-furyl.

Examples of the divalent fused cyclic group in the formula (b2-1) and the formula (b2-2) include a naphthyl group.

In the formula (b2-1), Y ⁵ is a single bond and R ⁵ is a compound having a carboxyl group, or Y ⁵ is a methyl group, an alkylene group, or a divalent aromatic group and R ⁵ is a group having a carboxyl group. compound of. b is preferably an integer of 0 to 2, and more preferably 1 or 2.

In formula (b2-2), R ⁷ is preferably a compound having a carboxyl group.

Specific examples of the compound represented by the formula (b2-1) include at least one of compounds represented by the formula (b2-1-1) to the formula (b2-1-24): Formula (b2-1-1) Formula (b2-1-2) Formula (b2-1-3) Formula (b2-1-4) Formula (b2-1-5) Formula (b2-1-6) Formula (b2-1-7) Formula (b2-1-8) Formula (b2-1-9) Formula (b2-1-10) Formula (b2-1-11) Formula (b2-1-12) Formula (b2-1-13) Formula (b2-1-14) Formula (b2-1-15) Formula (b2-1-16) (B2-1-17) Formula (b2-1-18) (B2-1-19) Formula (b2-1-20) Formula (b2-1-21) Formula (b2-1-22) Formula (b2-1-23) Formula (b2-1-24) R ¹ and R ^{8 in} formulas (b2-1-1) to (b2-1-24) have the same definitions as R ¹ and R ⁸ represented in formula (b2-1) , Z1 represents an integer from 1 to 10, and d is each independently an integer from 0 to 4.

Specific examples of the compound represented by the formula (b2-2) include at least one of compounds represented by the formula (b2-2-1) to the formula (b2-2-14): Formula (b2-2-1) Formula (b2-2-2) Formula (b2-2-3) Formula (b2-2-4) Formula (b2-2-5) Formula (b2-2-6) Formula (b2-2-7) Formula (b2-2-8) Formula (b2-2-9) Formula (b2-2-10) Formula (b2-2-11) Formula (b2-2-12) Formula (b2-2-13) Formula (b2-2-14)

R ³ and R ⁸ in formulae (b2-2-1) to (b2-2-14) are the same as R ³ and R ⁸ represented in formula (b2-2), and z2 represents an integer of 1 to 10, d are each independently an integer of 0 to 4.

Based on the total mole number of the second mixture being 1.0 mole, the cinnamic acid derivative (b2) is used in an amount of 0.05 to 0.4 mole, preferably 0.1 to 0.35 mole, more preferably 0.15 to 0.35 mole.

When the photo-alignable polysiloxane (B) does not contain a cinnamic acid derivative (b2), the liquid crystal alignment film formed by the prepared liquid crystal alignment agent has a low bulk impedance and a slow response speed. When the amount of the cinnamic acid derivative (b2) falls within the above range, the response speed of the liquid crystal alignment film formed by the prepared liquid crystal alignment agent can be further improved. Ethylene unsaturated compound ( b3 )

The ethylenically unsaturated compound (b3) has a structure represented by the formula (b3-1): Formula (b3-1) In formula (b3-1), R ¹⁰ is a straight or branched chain alkylene, phenylene, or cyclohexyl group having 1 to 10 carbon atoms, and a part of the hydrogen atom of R ¹⁰ is substituted Or not replaced. R ¹¹ is a linear or branched alkylene group having a carbon number of 1 to 10, and a part of the hydrogen atom of R ¹¹ is substituted or unsubstituted. R ¹² is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, and a part of the hydrogen atom of R ¹² is substituted or unsubstituted. R ¹³ is a hydrogen atom or a methyl group; L is -OCO-, -O-, or -S-. h is an integer from 0 to 10; K is 0 or 1; when K is 0, h is not 0; and when h is 2 or more, h of R and L ¹¹ are each the same or different.

Specifically, examples of the ethylenically unsaturated compound (b3) may include acrylic acid, methacrylic acid, 2-propenyloxyethyl-2-hydroxyethyl phthalic acid, and 4- (2-methyl-acrylic acid) ) Benzoic acid, 2-propenyloxyethylhexylhydrophthalic acid, 2-propenyloxyethylhexylhydrophthalic acid, 2-propenyloxyethylsuccinic acid, methacrylic acid Phthalic acid, phthalic acid monohydroxyethyl acrylate. One or more of the above examples can be used. Examples of commercially available products of the above compounds are acrylic acid and methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), Lightester HO-MS, Lightester HO-HH, HOA-MPL, HOA-MS, HOA-HH (Kyoeisha Chemical Co., Ltd.), M-5400 (East Asia Synthesis Co., Ltd.).

Specific examples of the ethylenically unsaturated compound (b3) may include compounds represented by the following formulae (b3-2) to (b3-17). Formula (b3-2) Formula (b3-3) (B3-4) (B3-5) Formula (b3-6) (B3-7) Formula (b3-8) Formula (b3-9) Formula (b3-10) (B3-11) Formula (b3-12) Formula (b3-13) (B3-14) (B3-15) (B3-16) (B3-17)

In the formulae (b3-11) to (b3-17), R ¹³ represents a hydrogen atom or a methyl group, t1 is an integer of 1 to 10, and t2 + t3 is an integer of 1 to 10.

Based on the total mole number of the second mixture being 1.0 mole, the amount of the ethylenically unsaturated compound (b3) used is 0.05 to 0.4 mole, preferably 0.1 to 0.35 mole, more preferably 0.15 to 0.35 mole.

When the photo-alignable polysiloxane (B) does not contain an ethylenically unsaturated compound (b3), the liquid crystal alignment film formed by the prepared liquid crystal alignment agent has a low bulk impedance and a slow response speed. When the amount of the ethylenically unsaturated compound (b3) falls within the above range, the response speed of the liquid crystal alignment film formed by the prepared liquid crystal alignment agent can be further improved. Carboxylic acid compound ( b4 )

The carboxylic acid compound (b4) includes a compound represented by the following formula (b4-1): W ¹ -W ² -W ³ Formula (b4-1) In formula (b4-1), W ¹ represents a carbon number of 4 to 20 An alkyl or alkoxy group, or a monovalent alicyclic organic group having 3 to 40 carbon atoms, wherein a part or all of the hydrogen atoms of the alkyl or alkoxy group described above may be substituted with a fluorine atom; W ² represents a single when a bond or phenylene, wherein, W ¹ is an alkoxy group, W ² is phenylene; W ³ represents a carboxylic acid group, a hydroxyl group, -SH, -NCO, -NHW ^e, wherein, W ^e represents a hydrogen atom or At least one of an alkyl group having 1 to 6 carbon atoms, -CH = CH ₂ and -SO ₂ Cl.

As W ¹ in the formula (b4-1), a preferable example is an alkyl or alkoxy group having 8 to 20 carbons, or a fluoroalkyl or fluoroalkoxy group having 4 to 20 carbons. As W ^2, the preferred embodiment is a single bond, 1,4-cyclohexylene or 1,4-phenylene. As W ³ , a preferred example is a carboxylic acid group.

Specific preferable examples of the compound represented by the formula (b4-1) are compounds represented by the formula (b4-1-1) to the formula (b4-1-4): C _H F _{2H + 1} -C _I H _2I- COOH formula (b4-1-1) Formula (b4-1-2) Formula (b4-1-3) Formula (b4-1-4)

In the above formula, H is an integer from 1 to 3; I is an integer from 3 to 18; J is an integer from 5 to 20; K is an integer from 1 to 3; M is an integer from 0 to 18; N is an integer from 1 to 18 Integer. Among them, specific preferred examples are compounds represented by the formula (b4-1-3-a) to the formula (b4-1-3-c). Formula (b4-1-3-a) Formula (b4-1-3-b) Formula (b4-1-3-c)

Specific examples of the carboxylic acid compound (b4) include butyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, capric acid, lauric acid, stearic acid, 4-propylbenzoic acid, and 4-butyl Benzoic acid, 4-pentylbenzoic acid, 4-hexylbenzoic acid, 4-heptylbenzoic acid, 4-octylbenzoic acid, 4-nonylbenzoic acid, 4-decylbenzoic acid, 4-dodecyl Benzoic acid, 4-octadecylbenzoic acid, 4-methoxybenzoic acid, 4-ethoxybenzoic acid, 4-propoxybenzoic acid, 4-butoxybenzoic acid, 4-pentoxybenzene Formic acid, 4-hexyloxybenzoic acid, 4-heptyloxybenzoic acid, 4-octyloxybenzoic acid, 4-nonyloxybenzoic acid, 4-decyloxybenzoic acid, 4-dodecyloxybenzoic acid , Octadecyloxybenzoic acid, 4- (4'-n-pentylcyclohexyl) benzoic acid, and compounds represented by the formulae (b4-2-1) to (b4-2-3). Formula (b4-2-1) Formula (b4-2-2) Formula (b4-2-3)

The total mole number of the monomers based on the second mixture is 1.0 mole, and the amount of the carboxylic acid compound (b4) used is ___ to ___ mole, preferably ___ to ___ mole, And more preferably ___ to ___ Mor. Method for manufacturing photo-alignable polysiloxane ( B )

The photo-alignable polysiloxane (B) can be obtained by converting an epoxy-containing polysiloxane (b1), a cinnamic acid derivative (b2), an ethylenically unsaturated compound (b3), and / or a carboxylic acid compound (b4). ) Reaction synthesis in the presence of a catalyst.

As the catalyst, an organic salt or a known compound such as a hardening accelerator that can accelerate the reaction between the epoxy compound and the acid anhydride can be used.

Examples of the organic salt include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; triethylamine, tri-n-propylamine, and tri-n-butylamine. Tertiary organic amines such as amines, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, and tertiary organic amines such as tetramethylammonium hydroxide. Among these organic amines, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine, or tetramethylammonium hydroxide, etc. are preferred. Grade organic amine.

Specific examples of the hardening accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethanolamine; Imidazole, 2-n-heptylimidazole, 2-n-alkylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl- 2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyano Ethyl) -2-5-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4- Methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis (hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2 -Phenyl-4,5-bis [(2'-cyanoethoxy) methyl] imidazole, l- (2-cyanoethyl-2-n-undecylimidazolium trimellitate , 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitic acid Salt, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-S-triazine, 2,4-diamino-6- (2'-n-deca Monoalkylimidazole Ethyl-S-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] ethyl-S-triazine, 2-methyl Trimeric isocyanate adduct of imidazole, trimeric isocyanate adduct of 2-phenylimidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] Imidazole compounds such as tri-isocyanate adducts of ethyl-S-triazine; organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenyl phosphite; benzyltriphenylphosphonium chloride ( benzyl triphenyl phosphonium chloride), tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyl Triphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium-O, O-diethylphosphonium dithiosulfate (tetra-n-butyl phosphonium-O, O-diethyl phosphorodithionate), tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetrabenzene Quaternary phosphonium salts such as diborates; 1,8-diazabicyclo [5.4.0] undec-7-ene or its organic acid salts, etc. Bicyclic olefins; organometallic compounds such as zinc octoate, tin octoate, aluminum acetylacetone complex; tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, Quaternary ammonium salts such as tetra-n-butylammonium chloride; boron compounds such as boron trifluoride and triphenyl borate; metal halogen compounds such as zinc chloride and tin tetrachloride; dicyandiamide (dicyandiamide) or high-melting dispersion latent hardening accelerators such as amine addition molding accelerators such as amine and epoxy resin adducts; the surface of the hardening accelerators such as imidazole compounds, organic phosphorus compounds or quaternary phosphonium salts Polymer-coated microcapsule type latent hardening accelerator; amine salt type latent hardening accelerator; Lewis acid salt, Bronsted acid salt and other high temperature dissociation type thermal cationic polymerization type Potential hardening accelerators such as latent hardening accelerators.

Specific examples of the hardening accelerator are preferably quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.

Based on 100 parts by weight of the photo-alignable polysiloxane (B), the amount of the catalyst used is 100 parts by weight or less, preferably 0.01 to 100 parts by weight, and more preferably 0.1 to 20 parts by weight.

The reaction temperature is preferably 0 ° C to 200 ° C, and more preferably 50 ° C to 150 ° C. The reaction time is preferably from 0.1 to 50 hours, and more preferably from 0.5 to 20 hours.

The synthesis reaction of the photo-alignable polysiloxane (B) can be performed in the presence of an organic solvent as required. The organic solvent is not particularly limited, and may be the same as or different from the organic solvent used in the production of the epoxy group-containing polysiloxane (b1) and the solvent (C) contained in the liquid crystal alignment agent of the present invention. the same. Specific examples of the organic solvent are preferably 2-butanone, 2-hexanone, methyl isobutyl ketone, n-butyl acetate, or a combination thereof.

The photo-alignable polysiloxane (B) has a polystyrene-equivalent weight average molecular weight as measured by Gel Permeation Chromatography (GPC) of 2,000 to 20,000, preferably 3,000 to 18,000, more It is preferably 5,000 to 15,000.

Based on 100 parts by weight of the polymer (A), 5 to 30 parts by weight of the photo-alignable polysiloxane (B), preferably 5 to 28 parts by weight, and more preferably 5 to 25 parts by weight Serving. Solvent ( C )

The solvent used in the liquid crystal alignment agent of the present invention is not particularly limited, as long as it dissolves the polymer (A), the photo-alignable polysiloxane (B) and other arbitrary components and does not react therewith, It is preferable that the solvent used in the synthesis of the polyamic acid is the same as the solvent used in the synthesis of the polyamino acid.

Specific examples of the solvent (C) include, but are not limited to, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, 4-hydroxy-4-methyl-2-pentanone, and ethylene glycol Monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, Ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Or N, N-dimethylformamide or N, N-dimethyl acetamide, etc. The solvent (C) can be used alone or in combination.

Based on 100 parts by weight of the polymer (A), 1500 to 4000 parts by weight of the solvent (C), preferably 1500 to 3800 parts by weight, and more preferably 1500 to 3500 parts by weight. Additive ( D )

To the extent that the efficacy of the present invention is not affected, the liquid crystal alignment agent may optionally add an additive (D), wherein the additive (D) includes a compound having at least two epoxy groups, a silane compound having a functional group, Or a combination.

Compounds having at least two epoxy groups include, but are not limited to, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-di Bromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl- M-xylenediamine, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4 '-Diaminodiphenylmethane, 3- (N, N-diepoxypropyl) aminopropyltrimethoxysilane, or a combination of the foregoing compounds.

The compound having at least two epoxy groups may be used alone or in combination.

The use amount of the compound having at least two epoxy groups may be 0 to 40 parts by weight, and preferably 0.1 to 30 parts by weight based on the use amount of the polymer (A).

Specific examples of the silane compound having a functional group include, but are not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2 -Aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Dimethoxysilane, 3-ureidopropyltrimethoxy silane, 3-ureidopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxy Silyl, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylene Triamine, 10-trimethoxysilyl-1,4,7-triazine, 10-triethoxysilyl-1,4,7-triazine, 9-trimethoxysilyl- 3,6-Diazinyl acetate, 9-triethoxysilyl-3,6-diazinyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl N-phenyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane , A combination -3- N- bis (oxyethylene) -3-aminopropyl trimethoxy Silane, N- bis (oxyethylene) aminopropyl triethoxysilane Silane, or the above compounds.

The silane compound having a functional group may be used alone or in combination.

Based on the use amount of the polymer (A) being 100 parts by weight, the use amount of the silane compound having a functional group may be 0 to 10 parts by weight, and preferably 0.5 to 10 parts by weight.

The use amount of the additive (D) is preferably 0.5 to 50 parts by weight, and more preferably 1 to 45 parts by weight based on the total use amount of the polymer (A). < Manufacturing method of liquid crystal alignment agent >

The method for producing the liquid crystal alignment agent of the present invention is not particularly limited, and it can be produced by a general mixing method. For example, the polymer (A) and the photo-alignable polysiloxane (B) manufactured in the above manner are first mixed uniformly to form a mixture. Next, the solvent (C) is added under the condition of a temperature of 0 ° C. to 200 ° C., and the additive (D) is optionally added, and finally, the stirring is continued with a stirring device until dissolved. In addition, it is preferable to add the solvent (C) at a temperature of 20 ° C to 60 ° C.

At 25 ° C, the viscosity of the liquid crystal alignment agent of the present invention is usually 15 cps to 35 cps, preferably 17 cps to 33 cps, and more preferably 20 cps to 30 cps. < Manufacturing method of liquid crystal alignment film >

After the liquid crystal alignment agent of the present invention is applied to a substrate, if necessary, a coating film obtained through pre-bake, post-bake, or other heat treatment is used as a liquid crystal alignment film. The coating film may be subjected to rubbing, irradiation with polarized light or light of a specific wavelength, or an ion beam, or ultraviolet rays may be irradiated while a voltage is applied to the liquid crystal display element after the liquid crystal is filled. Used as a surface control vertical alignment film.

In this case, the substrate used is not particularly limited as long as it is a substrate having high transparency. The substrate is, for example, a glass plate, polycarbonate, poly (meth) acrylate, polyether, polyarylate, polyurethane, polyfluorene, polyether, polyetherketone, trimethylpentene, polyolefin, Polyethylene terephthalate, (meth) acrylonitrile, cellulose triacetate, cellulose diacetate, or cellulose acetate butyrate, etc. From the viewpoint of simplification of the manufacturing process, the substrate is preferably a substrate on which an indium tin oxide (ITO) electrode for liquid crystal driving is formed. When the reflective liquid crystal display element is a single-sided substrate, an opaque material such as a silicon wafer may be used. In addition, an electrode at this time may be made of a material that reflects light.

The application method of the liquid crystal alignment agent is not particularly limited, and examples thereof include a printing method such as screen printing, offset printing, flexo printing, inkjet method, spraying method, and roller coating. Cloth, dipping, slit coating, spin coating, etc. From the viewpoint of productivity, the transfer printing method widely used in industry is also applicable to the present invention.

After the liquid crystal alignment agent is applied by the method described above, a coating film can be formed through pre-baking and post-baking treatments. Although the pre-baking step after applying the liquid crystal alignment agent is not necessary, it is preferable to further perform the pre-baking step when the substrates are not fixed after coating or when the substrates are not baked immediately after coating. . In this pre-baking step, the organic solvent may be volatilized to such an extent that the shape of the coating film is not deformed due to the transportation of the substrate or the like. The conditions for the pre-baking treatment are not particularly limited, and for example, it is performed at any temperature of 40 ° C to 150 ° C, preferably 50 ° C to 120 ° C, and more preferably 60 ° C to 100 ° C. The pre-baking treatment may be performed at any time from 0.1 minutes to 30 minutes, preferably from 0.5 minutes to 15 minutes, and more preferably from 1 minute to 5 minutes.

The conditions of the post-baking treatment are not particularly limited, and for example, it is performed at any temperature of 100 ° C to 350 ° C, preferably 120 ° C to 300 ° C, and more preferably 150 ° C to 250 ° C. The post-baking treatment may be performed at any time from 5 minutes to 240 minutes, preferably 10 minutes to 100 minutes, and more preferably 20 minutes to 90 minutes. The heating can be performed by a generally known method, for example, a heating plate, a hot-air circulation furnace, or an infrared furnace can be used for heating.

The thickness of the liquid crystal alignment film obtained after the post-baking is not particularly limited, and may be, for example, 1 to 1000 nm, preferably 5 to 500 nm, and more preferably 10 to 300 nm. <Liquid crystal display device and manufacturing method>

The liquid crystal display element of the present invention includes a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention. The liquid crystal display element of this invention can be manufactured as follows.

In detail, the liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method, and then fabricating a liquid crystal cell by a known method. Specific examples of the liquid crystal display element include, for example, a vertical alignment type liquid crystal display element including a liquid crystal cell. The liquid crystal cell includes: two substrates arranged opposite to each other, a liquid crystal layer provided between the substrates, and a substrate and the liquid crystal layer. The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is used.

Specifically, a vertical alignment type liquid crystal display element including a liquid crystal cell is prepared by applying the liquid crystal alignment agent of the present invention on two substrates, and pre-baking and post-baking The liquid crystal alignment film is formed by processing, and then the liquid crystal alignment film is arranged with two substrates facing each other, and a liquid crystal layer made of liquid crystal is held between the two substrates, that is, the liquid crystal layer is disposed in contact with the liquid crystal alignment film. Finally, a voltage is applied to the liquid crystal alignment film and the liquid crystal layer, and ultraviolet rays are irradiated at the same time.

As described above, the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is used to polymerize a polymerizable compound while irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, and at the same time to polymerize the polysiloxane The reactive unsaturated groups react with each other, or the polymerizable unsaturated group reacts with the polymerizable compound, so that the alignment of the liquid crystal can be more efficiently fixed, and a liquid crystal with excellent UV decay resistance and colorless phase unevenness can be formed. Display element.

The method of holding this liquid crystal layer between two substrates is, for example, the following two known methods:

(Method 1) A pair of substrates having a liquid crystal alignment film formed is prepared, and spacers such as beads are spread on the liquid crystal alignment film of one of the substrates, and the two liquid crystal alignment films are opposed to each other. Then, another substrate was bonded, and then the liquid crystal was injected under reduced pressure and sealed.

(Method 2) Prepare a pair of substrates with a liquid crystal alignment film, and spread spacers such as beads on the liquid crystal alignment film of one of the substrates, drop the liquid crystal, and then make the two liquid crystal alignment films reciprocate in an opposite manner. Laminate another substrate and seal it.

In the above two methods, the thickness of the spacer is preferably 1 to 30 μm, and more preferably 2 to 10 μm.

A step of applying a voltage to the liquid crystal alignment film and the liquid crystal layer while irradiating ultraviolet rays to produce a liquid crystal cell. For example, a voltage is applied between electrodes provided on a substrate to apply an electric field to the liquid crystal alignment film and the liquid crystal layer to maintain the state of the electric field. Under UV light. The voltage applied between the electrodes is, for example, 5 Vp-p to 30 Vp-p, and preferably 5 Vp-p to 20 Vp-p. The amount of ultraviolet irradiation is, for example, 1 J to 60 J, preferably 40 J or less, and more preferably 10 J or less. The smaller the amount of ultraviolet irradiation, the lower the reliability caused by the destruction of the liquid crystal or the material constituting the liquid crystal display element can be suppressed, and the manufacturing efficiency can be improved by reducing the ultraviolet irradiation time. According to the present invention, the reaction speed can be increased even with a small amount of ultraviolet irradiation, and therefore, even at a low irradiation amount of about 5 J, a liquid crystal display element having a sufficiently fast reaction speed can be formed.

In this way, when a voltage is applied to the liquid crystal alignment film and the liquid crystal layer and ultraviolet rays are simultaneously irradiated, the polymerizable compound can be reacted to form a polymer. In addition, the polymerizable unsaturated group of the polysiloxane can also be irradiated with ultraviolet rays. In this case, they react with each other or with a polymerizable compound. By the above reaction, the liquid crystal alignment film can obtain a better cured structure, so that the obtained liquid crystal display element has the properties of good resistance to ultraviolet decay and uneven coloring.

In addition, the above-mentioned liquid crystal alignment agent can be used not only as a liquid crystal alignment agent for manufacturing liquid crystal display elements of a vertical alignment method such as a surface-controlled vertical alignment type (SCVA) liquid crystal display, but also can be applied to those produced by rubbing treatment or light alignment treatment. Use of liquid crystal alignment film.

The liquid crystal includes a nematic liquid crystal or a dish-shaped liquid crystal. Specific examples of the liquid crystal include, but are not limited to, liquid crystals having positive dielectric anisotropy. For example, biphenyl-based liquid crystals, phenyl cyclohexane-based liquid crystals, Ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane- based liquid crystals), bicyclooctane-based liquid crystals, cubic-based liquid crystals, or a combination of the above liquid crystals. In addition, a cholesteric liquid crystal such as cholesteryl chloride, cholesteryl nonanoate, and cholesteryl carbonate may be further added to the liquid crystal; Chiral agents sold under the trade names "C-15" and "CB-15" (Merck); p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate (p -decyloxybenzylidene-p-amino-2-methyl butyl cinnamate) and other ferroelectric liquid crystals.

In addition, specific examples of the liquid crystal may include a liquid crystal having a negative dielectric anisotropy. For example, dicyanobenzene-based liquid crystal, pyridazine-based liquid crystal, Greek Schiff base-based liquid crystal, azoxy-based liquid crystal, biphenyl-based liquid crystal, phenyl cyclohexane-based liquid crystal liquid crystal), or a combination of the above liquid crystals.

The present invention will be further described with reference to the following examples, but it should be understood that these examples are merely illustrative and should not be construed as limitations of the implementation of the present invention. Synthesis example of polymer ( A )

The following describes Synthesis Examples A-1-1 to A-1-20, Synthesis Examples A-2-1 to A-2-2, and Synthesis Example A-3-1 of Polymer (A): Synthesis Example A-1- 1

A 500 ml four-necked conical flask was provided with a nitrogen inlet, a stirrer, a condenser tube, and a thermometer, and nitrogen was introduced. Then, in a four-necked conical flask, 4.32 g (0.04 mol) of p-diamine (abbreviated a2-3-1) and 2.42 g (0.01 mol) of the following formula (a2-3- The compound shown in 1-7) (abbreviated as a2-3-7) and 80 g of N-methyl-2-pyrrolidone (abbreviated as NMP) were stirred at room temperature until dissolved. Next, 11.2 g (0.05 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride (abbreviated as a1-1) and 20 g of NMP were added and reacted at room temperature for 2 hours. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, repeatedly washed with methanol and filtered three times, put into a vacuum oven, and dried at a temperature of 60 ° C. to obtain a polymer (A-1-1). Synthesis Examples A-1-2 to A-1-20

Synthesis Examples A-1-2 to A-1-20 were produced by the same steps as Synthesis Example A-1-1, and polymers (A-1-2) to (A-1-20) were different in that : Change the types of diamine compounds and tetracarboxylic dianhydride compounds and their amounts of use, as shown in Tables 1 and 2. Synthesis Example A-2-1

A 500 ml four-necked conical flask was provided with a nitrogen inlet, a stirrer, a condenser tube, and a thermometer, and nitrogen was introduced. Then, in a four-necked Erlenmeyer flask, 9.91 g (0.05 mol) of 4,4'-diaminodiphenylmethane (abbreviated as a2-3-2) and 80 g of NMP were added, and the solution was kept at room temperature. Stir until dissolved. Next, 11.2 g (0.05 mol) of a1-1 was added and reacted at room temperature for 2 hours. After the reaction is completed, 97 g of NMP, 2.55 g of acetic anhydride, and 7.91 g of pyridine are added, the temperature is raised to 60 ° C., and stirring is continued for 2 hours to perform the amidine imidization reaction. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, and repeatedly washed with methanol and filtered three times, put into a vacuum oven, and dried at a temperature of 60 ° C. to obtain a polymer (A-2-1). Synthesis Examples A-2-2 to A-2-5

Synthesis Examples A-2-2 to A-2-5 were used to produce polymers (A-2-2) to (A-2-5) in the same steps as in Synthesis Example A-2-1, but the difference was that : The parameter conditions for changing the types of diamine compounds and tetracarboxylic dianhydride compounds, their amounts of use, and hydrazone imidization parameters are shown in Table 2. Synthesis Example A-3-1

A 500 ml four-necked conical flask was provided with a nitrogen inlet, a stirrer, a condenser tube, and a thermometer, and nitrogen was introduced. Then, in a four-necked conical flask, (0.025 mol) of p-diaminebenzene (abbreviated as a2-3-1) and 40 g of NMP were added and stirred at room temperature until dissolved. Next, (0.025 mol) pyromellitic dianhydride (abbreviated as a1-3) and 10 g of NMP were added. After reacting at room temperature for 6 hours, 50 g of NMP, 1.3 g of acetic anhydride, and 10 g of pyridine were added, the temperature was raised to 60 ° C., and stirring was continued for 2 hours to carry out the imidization reaction. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, and repeatedly washed with methanol and filtered three times, put into a vacuum oven, and dried at a temperature of 60 ° C. to obtain a polymer (A-3-1-1).

A 500 ml four-necked conical flask was provided with a nitrogen inlet, a stirrer, a condenser tube, and a thermometer, and nitrogen was introduced. Then, in a four-necked conical flask, the above-mentioned synthesized polymer (A-3-1-1) and 0.015 mol of the compound represented by the formula (a2-1-11) (abbreviated as a2-1-4) were added. ), 0.01 mole of 9,9-bis (3-chloro-4-aminophenyl) hydrazone (abbreviated as a2-2-4) and 100 g of NMP, and stir at room temperature until dissolved. Next, 0.025 mole of 2,3,5-tricarboxycyclopentylacetic dianhydride (abbreviated as a1-1) and 10 g of NMP were added and reacted at room temperature for 2 hours. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, and repeatedly washed with methanol and filtered three times, put into a vacuum oven, and dried at a temperature of 60 ° C. to obtain a polymer (A-3-1).

The compounds corresponding to the abbreviations in Tables 1 and 2 are shown below.

[Table 1]

[Table 2] Synthesis example of photo-alignable polysiloxane ( B )

The following description of the light distribution isotropic silicon poly siloxane (B) Synthesis Example B-1 to B-12 and Comparative Synthesis Example B'-1 to B'-5: Synthesis Example B-1

A 500 ml three-necked flask was equipped with a stirrer, a condenser, and a thermometer. Then, in a three-necked flask, 0.6 mol of 2-glycidyletherethyltrimethoxysilane (hereinafter referred to as GETMS), 0.3 mol of methyltrimethoxysilane (hereinafter referred to as MTMS), and 0.1 mol Dimethyldimethoxysilane (hereinafter referred to as DMDMS) and 600 g of propylene glycol monomethyl ether (hereinafter referred to as PGME), and triethylamine (Triethylamine) was added within 30 minutes while stirring at room temperature , hereinafter abbreviated as TEA) solution (20 g TEA / 200 O ₂ g of H). Next, the three-necked flask was immersed in an oil bath at 30 ° C. and stirred for 30 minutes, and then the oil bath was heated to 90 ° C. within 30 minutes. When the internal temperature of the solution reached 75 ° C., the mixture was continuously heated and stirred for 6 hours . After the reaction is completed, the organic layer is taken out and washed with a 0.2% by weight ammonium nitrate aqueous solution to obtain a solution containing a polysiloxane compound.

Next, 0.10 mole of cinnamic acid derivative 5HBPA (abbreviated as b2-1), 0.10 mole of ethylenically unsaturated compound HOA-MPL (abbreviated as b3-1), and 0.05 mole of OCTBA (abbreviated as b4- 1) and 0.2 g of a hardening accelerator UCAT 18X (manufactured by SAN-APRO), and a solution containing a polysiloxane compound is added. Then, the three-necked flask was immersed in an oil bath at 30 ° C. and stirred for 10 minutes, and then the oil bath was heated to 115 ° C. within 30 minutes. When the internal temperature of the solution reached 100 ° C., heating and stirring were continued for 24 hours. After the reaction is completed, the organic layer is taken out, washed with water, dried with magnesium sulfate, and the solvent is removed to obtain a photo-alignable polysiloxane (B-1). Synthesis Examples B-2 to B-12 and Comparative Synthesis Examples B'-1 to B'-5

Synthesis Examples B-2 to B-12 and Comparative Synthesis Examples B'-1 to B'-5 In the same steps as in Synthesis Example B-1, photo-alignable polysiloxanes (B-2) to (B -12) and (B'-1) to (B'-5), the difference is that the epoxy group-containing silane compound, other silane compounds, cinnamic acid derivatives, ethylenically unsaturated compounds, solvents, The types of the mediators or hardening accelerators, their usage amounts, reaction temperatures, and polycondensation times are shown in Tables 3 and 4.

The compounds corresponding to the abbreviations in Tables 3 and 4 are shown below.

[table 3]

[Table 4] Examples and comparative examples of liquid crystal alignment agents, liquid crystal alignment films, and liquid crystal display elements

Examples 1 to 26 and Comparative Examples 1 to 9 of the liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element will be described below: a. Liquid crystal alignment agent

100 parts by weight of polymer (A-1-1), 5 parts by weight of photo-alignable polysiloxane (B-1), and 3,000 parts by weight of N-methyl-2-pyrrolidone (referred to as C- 1), and continue stirring with a stirring device at room temperature until dissolved, the liquid crystal alignment agent of Example 1 can be formed. b. Liquid crystal alignment film and liquid crystal display element

The prepared liquid crystal alignment agent was coated on the transparent electrode surface of a glass substrate containing an ITO film (the liquid crystal alignment film printer was manufactured by Japan Photo Printing Co., Ltd.), and heated on a hot plate at 80 ° C for 1 minute (pre-baking). ) After removing the solvent, it is heated on a hot plate at 150 ° C for 10 minutes (post-baking) to obtain a coating film with an average film thickness of 600 Å. The coating film was placed in a friction machine with a rayon cloth wound, and the rubbing treatment was performed at a rotation speed of 400 rpm, a traverse speed of 3 cm / second, and a fiber length of 0.1 mm. After that, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in an oven at 100 ° C. for 10 minutes to obtain a substrate having a liquid crystal alignment film. Repeat the foregoing steps to obtain a pair (2 pieces) of substrates with a liquid crystal alignment film.

Next, after one of the substrates having a liquid crystal alignment film is coated with an epoxy resin adhesive filled with alumina balls having a diameter of 5.5 μm, the other liquid crystal alignment film is superimposed in a surface-opposing manner. The adhesive hardens. Then, a nematic liquid crystal (Merck, MLC-6608) was filled from a pair of liquid crystal injection ports between the substrates, and then the liquid crystal injection ports were sealed with an acrylic photocuring adhesive, and ultraviolet light was used. The lamp shines to harden it. Next, an alternating current of 20 Vp-p was applied between the two ITO electrodes, and 3800 mJ / cm ² of ultraviolet light was irradiated while the liquid crystal was being driven, and then the liquid crystal display element of Example 1 was obtained.

The liquid crystal display element of Example 1 was evaluated by each evaluation method described later. The results are shown in Table 5. Examples 2 to 26

The liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element of Example 2 to Example 26 were separately manufactured in the same steps as in Example 1, and the difference was that the type of the component and its use amount were changed, as shown in Table 5, 6 shown. The liquid crystal display elements prepared in Examples 2 to 26 were evaluated in the evaluation method described later, and the results are shown in Tables 5 and 6. Comparative Examples 1 to 9

The liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element of Comparative Example 1 to Comparative Example 9 were separately manufactured in the same steps as in Example 1, except that the type of the component and the amount of use were changed, as shown in Table 7. . The liquid crystal display elements prepared in Comparative Examples 1 to 9 were evaluated in the evaluation method described later, and the results are shown in Table 7.

The compounds corresponding to the abbreviations in Tables 5 to 7 are shown below. Evaluation method a. Rate of imidization

The fluorene imidization ratio refers to the total number of fluorene imine functional groups and the number of fluorene imine rings in the polymer, and the ratio of the number of fluorene imine rings is calculated as a percentage.

The detection method is to separately dry the polymer of the synthesis example under reduced pressure, and then dissolve it in an appropriate deuteration solvent (for example: deuterated dimethylsulfine), using tetramethylsilane as a reference material, and ¹ H-NMR measurement results ^{(1 H-Nuclear magnetic resonance,} 1 H-NMR) at room temperature (e.g. 25 ℃), then from equation (1) can be obtained (PEI) ratio (%). Mathematical formula (1) Δ1: peak area generated by chemical shift of NH matrix proton around 10 ppm; Δ2: peak area of other protons; α: precursor of polymer (polyamic acid) The ratio of the number of one proton of the NH group to the other protons in the NH group. b. body impedance

The prepared liquid crystal alignment agent was dropped into an aluminum dish with a diameter of 32 mm and baked on a hot plate to obtain a film having a film thickness of about 0.01 mm. Continue to measure the resistance value of the film with a resistance meter (AGILENT 4339b High resistance meter), clamp the positive and negative electrodes of the instrument to both ends of the aluminum plate containing the film, and record the measured resistance value at a voltage of 50 volts. Its evaluation standard As follows: ○: resistance value ≧ 1.0x10 ¹⁵ ; ╳: resistance value ≦ 1.0x10 ¹⁵ . c. response speed

First, the liquid crystal display elements of each Example and Comparative Example were irradiated with a visible light lamp without applying a voltage, and the brightness of the light penetrating the liquid crystal display element at this time was measured with a photomultiplier tube, and the liquid crystal display was penetrated at this time. The brightness of the light of the element was set to a relative light transmittance of 0%. Next, the same test was performed on the liquid crystal display element under the application of an AC voltage of 10 V for 5 seconds, and the brightness of the light penetrating the liquid crystal display element at this time was set to a relative transmittance of 100%. Then, the same test was performed on the liquid crystal display element under the application of an AC voltage of 3.5 V, and the time elapsed from the relative transmittance of 10% to 90% was measured. The elapsed time was defined as the response speed of the liquid crystal display element. The evaluation criteria are as follows: ：: response speed ≦ 10 msec; ○: 10 msec <response speed ≦ 20 msec; ╳: response speed> 20 msec.

[table 5]

[TABLE 6]

[TABLE 7] ＜ Evaluation results ＞

From Tables 5 to 7, it is known that the liquid crystal alignment film formed by the liquid crystal alignment agent (Example 1 to Example 26) having a specific photo-alignment polysiloxane has a fast response speed and a high body impedance.

On the other hand, since the liquid crystal alignment agents of Comparative Examples 1 to 9 did not have a specific photo-alignment polysiloxane, the response speed and bulk impedance evaluation of Comparative Examples 1 to 9 were not good.

In addition, when the diamine component (a2) of the polymer (A) in the liquid crystal alignment agent contains the diamine compound (a2-1) (Examples 5-14, 19, 20, 23, 25), the liquid crystal The alignment film exhibits better body impedance.

In addition, when the diamine component (a2) of the polymer (A) in the liquid crystal alignment agent contains a diamine compound (a2-2) having a fluorene group (Examples 15-20, 24, 25), the liquid crystal The bulk impedance performance of the alignment film is also better.

In addition, when the amount of the cinnamic acid derivative (b2) of the photo-alignable polysiloxane (B) in the liquid crystal alignment agent falls within a specific range (Example 1-26), the liquid crystal produced can be further improved. The response speed of the liquid crystal alignment film formed by the alignment agent.

In addition, when the use amount of the ethylenically unsaturated compound (b3) of the photo-alignable polysiloxane (B) in the liquid crystal alignment agent falls within a specific range (Examples 1-26), the prepared product can be further improved. The response speed of the liquid crystal alignment film formed by the liquid crystal alignment agent.

In summary, since the liquid crystal alignment agent of the present invention has a specific photo-alignment polysiloxane (B), it can improve the response speed of the liquid crystal display element and has a high body impedance.

When the diamine component (a2) of the polymer (A) in the liquid crystal alignment agent of the present invention contains a diamine compound (a2-1) or a diamine compound (a2-2) having a fluorenyl group, Can further increase the bulk impedance of the liquid crystal alignment film.

In addition, when the amount of the cinnamic acid derivative (b2) or the ethylenically unsaturated compound (b3) of the photo-alignable polysiloxane (B) in the liquid crystal alignment agent falls within a specific range, the prepared product can be further improved. Response speed of a liquid crystal alignment film formed by a liquid crystal alignment agent.

Although the present invention has been disclosed as above with the examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application.

no

no.

Claims (14)

A liquid crystal alignment agent includes: a polymer (A); a photo-alignable polysiloxane (B); and a solvent (C). The polymer (A) is prepared by reacting a first mixture. The first The mixture includes a tetracarboxylic dianhydride component (a1) and a diamine component (a2); the photo-alignable polysiloxane (B) is derived from an epoxy-containing polysiloxane (b1) and cinnamic acid The compound (b2) is obtained by reacting with an ethylenically unsaturated compound (b3). The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the epoxy group-containing polysiloxane (b1) includes a group represented by the formula (b1-1) and a group represented by the formula (b1-2) At least one of a base and a base represented by formula (b1-3): Formula (b1-1) In formula (b1-1), B represents an oxygen atom or a single bond; m represents an integer from 1 to 3; n represents an integer from 0 to 6, wherein when n represents 0, B is a single bond; * Indicates the junction, Formula (b1-2) In formula (b1-2), p represents an integer from 0 to 6; * represents a bond, Formula (b1-3) In formula (b1-3), D represents an alkylene group having 2 to 6 carbon atoms; E represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; * represents a bond. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the epoxy group-containing polysiloxane (b1) includes a copolymer obtained by hydrolyzing and partially condensing a second mixture, and the first The two mixtures include an epoxy group-containing silane compound (b1-1), which has a structure represented by the formula (b1-4): Si (R _x ) _w ( OR _y ) _4-w Formula (b1-4) In formula (b1-4), R _x represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 6 carbon atoms. An aryl group, an epoxy-containing alkyl group, or an epoxy-containing alkoxy group, and at least one R _x is an epoxy-containing alkyl group or an epoxy-containing alkoxy group; when w is 2 or higher, one R _x w are each the same or different; R _y represents a hydrogen atom, alkyl having 1 to 6 carbon atoms or acyl of 1 to 6 carbon atoms, an aryl group having 6 to 15; when w When it is 2 or less, (4-w) R _y are each the same or different; w represents an integer of 1 to 3. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the cinnamic acid derivative (b2) is selected from the group consisting of compounds represented by formula (b2-1) and formula (b2-2) At least one of: Formula (b2-1) Formula (b2-2) In formulas (b2-1) and (b2-2), R represents a fluorine atom or a cyano group; a represents an integer of 0 to 4; R ¹ and R ³ each independently represent a hydrogen atom and a carbon number An alkyl group having 1 to 40 or a monovalent alicyclic organic group having 3 to 40 carbon atoms, and a part or all of the hydrogen atoms of the alkyl group may be substituted by fluorine atoms; R ² and R ⁴ each independently represent two Valent aromatic group, divalent alicyclic group, divalent heterocyclic group or divalent fused ring group, and R ² or R ⁴ is an unsubstituted or at least part of a hydrogen atom R ⁸ is substituted, the R ⁸ each independently represent a halogen atom, a nitro group, a cyano group, an alkyl group having a carbon number of 1 to 5 carbon atoms or an alkoxy group having 1 to 5, said alkyl group or said alkyl Oxygen is unsubstituted or at least part of the hydrogen atoms are replaced by halogen; Y ¹ , Y ² , Y ⁴ each independently represents a single bond, an oxygen atom, -COO- or -OCO-; Y ⁵ represents a single bond, and the carbon number is 1 to 10 alkylene, 2 to 10 carbon or 2 divalent aromatic group; when Y ⁵ represents a single bond, e represents 1 and R ⁵ represents a hydrogen atom; when Y ⁵ represents carbon Alkylene number 1 to 10, carbon number 2 When alkenylene group or a divalent aromatic group 10, e represents 0 or 1, and R ⁵ represents a carboxylic acid group, a hydroxyl ^{group, -SH, -NCO, -NHR ',} -CH = CH 2 or -SO ₂ Cl R ^′ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Y ³ represents an oxygen atom or a divalent aromatic group; R ⁶ represents a divalent aromatic group, a divalent heterocyclic group, or a divalent thick Cyclic group; Y ⁶ represents an oxygen atom, -COO- or -OCO-; R ⁷ represents a carboxylic acid group, a hydroxyl group, -SH, -NCO, -NHR ^'' , -CH = CH ₂ or -SO ₂ Cl , R ^'' represents a hydrogen atom or an alkyl group having a carbon number of 1 to 6; Y ⁷ represents a single _{bond, -OCO- (CH 2) i -} * , or _{-O- (CH 2) j - *} , where i and j Each independently represents an integer of 1 to 10, and * each independently represents a bond with R ⁷ ; b, c, and f each independently represent an integer of 0 to 3. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the ethylenically unsaturated compound (b3) has a structure represented by the formula (b3-1): Formula (b3-1) In formula (b3-1), R ¹⁰ is a linear or branched alkylene, phenylene, or cyclohexyl group having 1 to 10 carbon atoms, and a part of the hydrogen atom of R ¹⁰ Substituted or unsubstituted; R ¹¹ is a straight or branched chain alkylene group having 1 to 10 carbon atoms, and a part of hydrogen atoms of R ¹¹ is substituted or unsubstituted; R ¹² is a single bond, carbon number A linear or branched alkylene group of 1 to 10, a part of the hydrogen atom of R ¹² is substituted or unsubstituted; R ¹³ is a hydrogen atom or a methyl group; L is -OCO-, -O-, or- -S-; h is an integer from 0 to 10; k is 0 or 1; when k is 0, h is not 0; and when h is 2 or more, h of R and L ¹¹ are each the same or different. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the diamine component (a2) includes a diamine compound (a2-1), and the diamine compound (a2-1) is selected from the formula ( a2-1-1), at least one of the groups consisting of compounds represented by formula (a2-1-2) and formula (a2-1-3): Formula (a2-1-1) Formula (a2-1-2) Formula (a2-1-3) In formulas (a2-1-1) to (a2-1-3), X represents a single bond, -COO-, -CONR _d -or -R _e -NR _d- ; R _a is a single bond or a linear or branched alkyl group having 1 to 10 carbons; R _b is a linear or branched alkoxy group, nitrile group, or carbonyl group having 1 to 10 carbons; R _c is a carbon number of 1 to 10 straight or branched alkyl groups; or R _b and R _c combine with each other to form a single ring; R _d is a hydrogen atom or a straight or branched alkyl group having 1 to 10 carbon atoms; R _e is a single bond Or a linear or branched alkyl group having 1 to 10 carbon atoms; a1 is 0 or 1; a2 is an integer from 0 to 2; when X is a single bond, a1 is 0; when X is -COO-, -CONR _{When d} -or -NR _d- , a1 is 1. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the diamine component (a2) includes a diamine compound (a2-2) having a fluorenyl group. The liquid crystal alignment agent according to item 3 of the scope of patent application, wherein the total mole number of the second mixture is 1.0 mole, and the usage amount of the epoxy-containing silane compound (b1-1) is 0.6 To 1.0 Mor. The liquid crystal alignment agent according to item 3 of the scope of patent application, wherein based on the total mole number of the second mixture being 1.0 moles, the cinnamic acid derivative (b2) is used in an amount of 0.05 to 0.4 moles, The amount of the ethylenically unsaturated compound (b3) used is 0.1 to 0.4 mole. The liquid crystal alignment agent according to item 6 of the scope of patent application, wherein the total mole number based on the diamine component (a2) is 1.0 mole, and the usage amount of the diamine compound (a2-1) is 0.2 To 0.6 mol. The liquid crystal alignment agent according to item 7 of the scope of patent application, wherein based on the total mole number of the diamine component (a2) is 1.0 mole, the diamine compound (a2-2) having a fluorenyl group The amount used is 0.2 to 0.6 mol. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the photo-alignable polysiloxane (B) is used in an amount of 5 to 30 based on 100 parts by weight of the polymer (A) used. Parts by weight; the solvent (C) is used in an amount of 1500 to 4000 parts by weight. A method for manufacturing a liquid crystal alignment film includes: a step of applying the liquid crystal alignment agent according to any one of items 1 to 12 of a patent application scope on a substrate. A liquid crystal display element includes: a liquid crystal alignment film prepared by the method for manufacturing a liquid crystal alignment film according to item 13 of the scope of patent application.